CN101342115A - Nano-hydroxyapatite glycerin cement, preparation method and application in toothpaste thereof - Google Patents
Nano-hydroxyapatite glycerin cement, preparation method and application in toothpaste thereof Download PDFInfo
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- CN101342115A CN101342115A CNA2008100302453A CN200810030245A CN101342115A CN 101342115 A CN101342115 A CN 101342115A CN A2008100302453 A CNA2008100302453 A CN A2008100302453A CN 200810030245 A CN200810030245 A CN 200810030245A CN 101342115 A CN101342115 A CN 101342115A
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Abstract
The invention relates to a preparation method for a nanometer hydroxyapatite glycerin cement, which comprises: step one, calcium agents are grinded and screened by a screen with 300 meshes to obtain calcium powders, ethanol and glycerol are mixed by the mass ratio of 0.1 to 1.5: 1, and are added with the calcium powders to stir evenly to obtain A component; wherein, the calcium content is 1 to 20wt percent; step two, the ethanol and the glycerol are mixed by the mass ratio of 0 to 1:1, and are added with concentrated phosphoric acid solution with 85 percent of mass percent concentration by the mass ratio of 1:2 to 10 to stir evenly to obtain B component; step three, the A component is loaded in a reaction kettle to be stirred and heated up to slightly boil for 20 to 30 minutes, is added with the B component into the reaction kettle to stop the adding when the PH value of the mixture reaches 8 to 8.5, the reaction continues for 3 to 6 hours under the slight boiling; step four, the mixture solution in the reaction kettle is distilled to the mixture solution with ethanol content less than 0.5 wt percent to obtain the nanometer hydroxyapatite glycerin cement. The method has simple process, the nanometer hydroxyapatite in the product has small particle diameter and can be used for preparing toothpaste.
Description
Technical field
The present invention relates to nano-hydroxyapatite glycerin cement and preparation method thereof and the application in toothpaste.
Background technology
Dental caries and periodontal disease are two kinds of multiple oral diseases, the serious harm human beings'health.Utilizing toothpaste to prevent and treat oral disease is a convenient valid approach.But the anticarious tooth paste overwhelming majority in the market is a toothpaste with fluoride, and fluorine can reduce enamel dissolubility, promotion enamel remineralization, influences the metabolism of oral cavity bacterium growth and sugar, control dental caries and periodontal disease are had obvious effect.But fluorine also be human body to the very sensitive trace element of its content, be more or less the same the amount that causes poisoning from satisfying the demand to, excessive fluorine absorption can cause filemot dental fluorosis, also can cause fluorosis and skeletal fluorosis when serious.China is the endemia fluorosis district occurred frequently, and except that Shanghai, the fluorosis area almost has in each province.Add up according to Ministry of Public Health Department of Disease Control: national water type fluorosis county in 2004 has 1117, pollution that caused by coal burning type fluorosis county 201.The geographic people of high fluorine often use toothpaste with fluoride beyond doubt very inappropriate, therefore press for to seek the fluorine substitution material and be used to produce floride-free anti-dental caries toothpaste.Hydroxyapatite is the main component of vertebrates skeleton and tooth, has good chemical stability and biocompatibility.Nanometer hydroxyapatite has characteristics such as high surface energy, high electrostatic field, strong polarization force, and enamel and cementum are had high affinity, can promote the enamel surface remineralization, improves dentium nitor face microhardness, strengthens the resistance to acid, tooth-whitening; Nanometer hydroxyapatite can also adsorb aminoacid and polysaccharide such as protein, glucosan in addition, destroys the formation of cariogenic bacteria speckle.The performance that these of nanometer hydroxyapatite are outstanding has caused the common concern of people to its application in toothpaste.Wherein, it is raw material that Meng Xiang just waits " nanometer hydroxyapatite and preparation method and the application in toothpaste " (number of patent application 02160058.9) of invention to adopt calcium hydroxide and dalcium biphosphate, by adding in the hydroxyapatite colloidal sols and powder body adding toothpaste of nucleating agent prepared sizes less than 100nm.And in another patent " application of acicular nanometer hydroxyapatite in toothpaste " (number of patent application 200410043880.7), the inventor joins the acicular nanometer hydroxyapatite of size less than 50nm in the toothpaste, reached repair teeth, preventing decayed tooth, desensitization effect better, but the preparation method of its unexposed nanometer hydroxyapatite." a kind of preparation method of activity hydroxy agustite tooth-paste " (number of patent application 200510096305.8) of invention such as Zhang Chaowu is that feedstock production obtains hydroxy apatite powder with calcium hydroxide and phosphoric acid, joins in the toothpaste through high-temperature calcination." a kind of nanoscale toothpaste additive and synthetic method " (number of patent application 200410046143.2) of Liu Jie invention adopts sol-gel process to prepare a kind of strontium and replaces the nanometer hydroxyapatite toothpaste additive.Though can both prepare the toothpaste that contains nanometer hydroxyapatite, can not satisfy simultaneously all that raw material is cheap, preparation is simple, particle diameter tiny (full-size is less than 50nm), good dispersion, add requirement easily by above-mentioned technology.Toothpaste is a kind of popular consumer goods, and is cheap, complicated preparation and dispersion technology, and use the unnecessary additive of toothpaste all can increase product cost, influence it and apply.
Summary of the invention
For the shortcoming and deficiency that overcomes prior art, the invention discloses a kind of preparation method of nano-hydroxyapatite glycerin cement, this method technology is simple, contain hydroxyapatite and toothpaste commonly used replenish the calcium caries preventive agent---the calcium glycerophosphate of particle diameter in the nano-hydroxyapatite glycerin cement for preparing according to this method, need not carry out special dispersion treatment and just can add in the toothpaste easily less than 50nm.
For realizing that purpose of the present invention adopts following technical scheme: a kind of preparation method of nano-hydroxyapatite glycerin cement comprises the steps:
The first step is pulverized calcium preparation, crosses 300 mesh sieves, gets the calcium preparation powder; By mass ratio is 0.1～1.5: 1 mixed ethanol and glycerol, ethanol glycerol mixed liquor; Add described calcium preparation powder in ethanol glycerol mixed liquor, stir and make the A component, wherein the content of calcium preparation is 1～20wt% in the A component;
Second step was 0～1: 1 mixed glycerol and ethanol by mass ratio, the glycerol alcohol mixeding liquid; With mass percent concentration is that 85% concentrated phosphoric acid adds in the glycerol alcohol mixeding liquid, stirs and makes the B component, and wherein the mass ratio of phosphoric acid and glycerol alcohol mixeding liquid is 1: 2～10;
The 3rd step, the A component is packed in the reactor, stir and be warming up to little boiling, after 20～30 minutes, the B component is slowly joined in the reactor, the pH value of mixed liquor is stabilized at 8.0～8.5 o'clock and stops to add the B component in reactor, and little boiling continued reaction 3～6 hours down;
The 4th step in the mixed liquor suction distilling apparatus in the described reactor, was distilled to ethanol content≤0.5wt%, got nano-hydroxyapatite glycerin cement.
More specifically, the calcium preparation in the described first step is calcium oxide or calcium hydroxide.
Calcium preparation in the described first step is the mixture of a kind of and calcium oxide or calcium hydroxide in the oxide of the oxide of oxide, zinc of strontium and magnesium; In the mixture, the mol ratio of strontium, zinc or magnesium and calcium is 0.02～0.5: 1.
Calcium preparation in the described first step is the mixture of a kind of and calcium oxide or calcium hydroxide in the hydroxide of the hydroxide of hydroxide, zinc of strontium and magnesium; In the mixture, the mol ratio of strontium, zinc or magnesium and calcium is 0.02～0.5: 1.
In order to realize the present invention better, in the described first step be 0.5～1: 1 mixed ethanol and glycerol by mass ratio, the content of calcium preparation is 5～15wt% in the A component.
Distilling apparatus in described the 4th step is a distillation column; Described distillation refers to air-distillation or distilling under reduced pressure.
Tower top temperature is 78～78.5 ℃ during described air-distillation.
A kind of nano-hydroxyapatite glycerin cement that makes according to the preparation method of above-mentioned nano-hydroxyapatite glycerin cement comprises that particle diameter is nanometer hydroxyapatite particle, calcium glycerophosphate, the G ﹠ W of 20～50nm.
Above-mentioned nano-hydroxyapatite glycerin cement prepares toothpaste as the glycerin component in the toothpaste by known method.
The nanometer hydroxyapatite that joins in the toothpaste accounts for 2～6% of toothpaste gross mass; The calcium glycerophosphate that adds in the toothpaste accounts for 0.05～1.5% of toothpaste gross mass.
Principle of the present invention is such:
Calcium oxide and calcium hydroxide all can generate weak base glycerol calcium and water with glycerine reaction, and this reaction is at room temperature slower, and elevated temperature and adding strontium salt catalyst can be accelerated reaction process.Phosphoric acid and glycerol calcium react in alcoholic solution and can generate tiny, the finely disseminated hydroxyapatite of particle diameter.In addition, phosphoric acid can generate phosphoglyceride with glycerine reaction when higher temperature, then generates phosphoglycerol calcium when calcium oxide or calcium hydroxide exist.Above-mentioned reaction can be expressed as:
CaO+C
3H
5(OH)
3→C
3H
5OHO
2Ca+H
2O
Ca(OH)
2+C
3H
5(OH)
3→C
3H
5OHO
2Ca+H
2O
C
3H
5OHO
2Ca+H
3PO
4+H
2O→Ca
10(PO
4)
6(OH)
2+C
3H
5(OH)
3
H
3PO
4+C
3H
5(OH)
3+Ca(OH)
2→CaC
3H
5(OH)
2PO
4+H
2O
H
3PO
4+C
3H
5(OH)
3+CaO→CaC
3H
5(OH)
2PO
4+H
2O
Above-mentioned being reflected in glycerol-alcoholic solution carried out, and wherein ethanol can play the effect of diluent and solvent.
The existence of glycerol and salt can destroy water and alcoholic acid constant boiling point, can adopt distillatory method to distill out dehydrated alcohol, can obtain comprising the nano-hydroxyapatite glycerin cement of nanometer hydroxyapatite particle, calcium glycerophosphate, G ﹠ W.
With respect to prior art major advantage of the present invention and beneficial effect be: simple, easy and simple to handle, the required raw material of the preparation method technology of (1) nano-hydroxyapatite glycerin cement disclosed by the invention is cheap and easy to get; (2) nano-hydroxyapatite glycerin cement that makes according to preparation method disclosed by the invention contains nanometer hydroxyapatite and the dual preventing decayed tooth component of calcium glycerophosphate, the hydroxyapatite granularity is little, reached nanoscale, need not carry out special dispersion treatment and just can add easily in the toothpaste, save the operation such as washing, filtration, drying of time-consuming power consumption in the nano powder preparation process; (3) the nano-hydroxyapatite glycerin cement solid content that makes according to preparation method disclosed by the invention reaches 20%, stores 60 days still good dispersions, and the solvent glycerin that wherein comprises also is to produce the primary raw material of toothpaste, utilization rate height; (4) ethanol of preparation method use disclosed by the invention can be recycled, and whole process of preparation does not have the three wastes and produces.
Description of drawings
Fig. 1 is the XRD figure of solid matter in the nano-hydroxyapatite glycerin cement for preparing of embodiment 1;
Fig. 2 is that the nano-hydroxyapatite glycerin cement that embodiment 1 prepares is schemed with the dispersive TEM of ethanol dilution.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
Among the following embodiment, it is 85% concentrated phosphoric acid that strong phosphoric acid all adopts mass percent concentration commonly used.
Embodiment 1
The first step, 0.9kg pulverizes with calcium hydroxide, crosses 300 mesh sieves, gets the calcium hydroxide powder; By mass ratio is 0.6: 1 mixed ethanol and glycerol, makes 12kg ethanol glycerol mixed liquor; Described powder is added in the ethanol glycerol mixed liquor, evenly make the A component in stirring at room;
Second step added concentrated phosphoric acid in the ethanol, stirred and made the B component, and wherein phosphoric acid and alcoholic acid mass ratio are 1: 10;
The 3rd step, with the A component pack into take back stream device the 25L reactor in, stirring is warming up to little boiling, after 30 minutes, first quick and back slow add in reactor by 2～20ml/min the B component, the pH of mixed value stabilization stopped at 8.5 o'clock adding in the question response still, continued reaction 4 hours, and course of reaction keeps little and boils and stir;
In the 4th step, with the suction distillation column while hot of the mixed liquor in the described reactor, normal pressure control tower top temperature down is 78.5 ℃ and distills, and is distilled to stop when ethanol content is for 0.3wt% in the bottoms, and the discharging cooling promptly gets nano-hydroxyapatite glycerin cement.
The nano-hydroxyapatite glycerin cement that makes is made toothpaste by known toothpaste production technology, and the raw material that wherein prepares toothpaste is made of by mass percent following material: nano-hydroxyapatite glycerin cement 30, CMC1.0, K
121.7, CaHPO
445, saccharin sodium 0.2, essence 1.0, distilled water 21.1.After measured, nanometer hydroxyapatite content is that 4.8wt%, calcium glycerophosphate are about 0.2wt% in the prepared toothpaste.
In the nano-hydroxyapatite glycerin cement that makes the XRD figure of solid matter as shown in Figure 1, by the shown characteristic of its XRD figure as can be known, the solids in the obtained colloid is weak crystalline hydroxy apatite.
Prepared nano-hydroxyapatite glycerin cement is schemed as shown in Figure 2 with the dispersive TEM of ethanol dilution, and as seen from Figure 2, in the prepared nano-hydroxyapatite glycerin cement colloid, the hydroxyapatite microscopic pattern is granular, and particle diameter is less than 50nm.
Embodiment 2
The first step with pulverizing after calcium hydroxide 0.85kg and the eight water Strontium hydrate. 0.15kg mixing, is crossed 300 mesh sieves, gets the powder of calcium hydroxide and eight water Strontium hydrate. mixture; By mass ratio is 1: 1 mixed ethanol and glycerol, makes 12kg ethanol glycerol mixed liquor; Described powder is added in the ethanol glycerol mixed liquor, evenly make the A component in stirring at room;
Second step added concentrated phosphoric acid in the ethanol, stirred and made the B component, and wherein phosphoric acid and alcoholic acid mass ratio are 1: 5;
The 3rd step, with the A component pack into take back stream device the 25L reactor in, stirring is warming up to little boiling, after 30 minutes, first quick and back slow add in reactor by 2～10ml/min the B component, the pH of mixed value stabilization stopped at 8.0 o'clock adding in the question response still, continued reaction 4 hours, and course of reaction keeps little and boils and stir;
In the 4th step, with the suction distillation column while hot of the mixed liquor in the described reactor, normal pressure control tower top temperature down is 78.5 ℃ and distills, and stops during for 0.48wt% up to the bottoms ethanol content, and the discharging cooling promptly gets nano-hydroxyapatite glycerin cement.
The nano-hydroxyapatite glycerin cement that makes is made toothpaste by known toothpaste production technology, and the raw material that wherein prepares toothpaste is made of by mass percent following material: nano-hydroxyapatite glycerin cement 28, CMC1.2, K
122.0, CaCO
345, tetrasodium pyrophosphate 1.0, saccharin sodium 0.2, essence 1.0, distilled water 21.6.After measured, containing strontium doping nanometer hydroxyapatite content in the toothpaste that makes is that 5.4wt%, calcium glycerophosphate are about 0.2wt%.
Embodiment 3
The first step, 0.7kg pulverizes with calcium oxide, crosses 300 mesh sieves, gets lime powder; By mass ratio is 1: 1 mixed ethanol and glycerol, makes 12kg ethanol glycerol mixed liquor; Described powder is added in the ethanol glycerol mixed liquor, evenly make the A component in stirring at room;
Second step was 0.5: 1 mixed glycerol and an ethanol by mass ratio, the glycerol alcohol mixeding liquid; Concentrated phosphoric acid is added in the glycerol ethanol, stir and make the B component, wherein the mass ratio of phosphoric acid and glycerol alcohol mixeding liquid is 1: 10;
The 3rd step, with the A component pack into take back stream device the 25L reactor in, stirring is warming up to little boiling, after 30 minutes, first quick and back slow add in reactor by 2～10ml/min the B component, the pH of mixed value stabilization stopped at 8.5 o'clock adding in the question response still, continued reaction 5 hours, and course of reaction keeps little and boils and stir;
In the 4th step, with the suction distillation column while hot of the mixed liquor in the described reactor, normal pressure control tower top temperature down is 78.5 ℃ and distills, and stops during for 0.45wt% up to the bottoms ethanol content, and the discharging cooling promptly gets nano-hydroxyapatite glycerin cement.
The nano-hydroxyapatite glycerin cement that makes is made toothpaste by known toothpaste production technology, and the raw material that wherein prepares toothpaste is made of by mass percent following material: nano-hydroxyapatite glycerin cement 30, methylcellulose 0.8, hydroxyethyl-cellulose 0.4, K
121.7, a-hydrated alumina 38, colloidal silica 5, methyl P-hydroxybenzoic acid sodium 2.5, tetrasodium pyrophosphate 7.5, allantoin 2.5, essence 1.0, distilled water 10.6.After measured, nanometer hydroxyapatite content is that 5.0wt%, calcium glycerophosphate are about 0.22wt% in the prepared toothpaste.
Embodiment 4
The first step with pulverizing after calcium hydroxide 0.55kg and the magnesium hydroxide 0.1kg mixing, is crossed 300 mesh sieves, gets the powder of calcium hydroxide and magnesium hydroxide mixture; By mass ratio is 1.5: 1 mixed ethanol and glycerol, makes 12kg ethanol glycerol mixed liquor; Described powder is added in the ethanol glycerol mixed liquor, evenly make the A component in stirring at room;
Second step added concentrated phosphoric acid in the ethanol, stirred and made the B component, and wherein phosphoric acid and alcoholic acid mass ratio are 1: 8;
The 3rd step, with the A component pack into take back stream device the 25L reactor in, stirring is warming up to little boiling, after 20 minutes, first quick and back slow add in reactor by 2～10ml/min the B component, the pH of mixed value stabilization stopped at 8.0 o'clock adding in the question response still, continued reaction 3 hours, and course of reaction keeps little and boils and stir;
In the 4th step, with the suction distillation column while hot of the mixed liquor in the described reactor, normal pressure control tower top temperature down is 78.5 ℃ and distills, and stops during for 0.49wt% up to the bottoms ethanol content, and the discharging cooling promptly gets nano-hydroxyapatite glycerin cement.
The nano-hydroxyapatite glycerin cement that makes is made toothpaste by known toothpaste production technology, and the raw material that wherein prepares toothpaste is made of by mass percent following material: nano-hydroxyapatite glycerin cement 28, CMC1.2, K
122.0, CaCO
345, tetrasodium pyrophosphate 1.0, saccharin sodium 0.2, essence 1.0, distilled water 21.6.After measured, containing the nano hydroxylapatite doped content of magnesium in the toothpaste that makes is that 4.8wt%, calcium glycerophosphate are about 0.2wt%.
Embodiment 5
The first step with pulverizing after calcium hydroxide 0.85kg and the zinc hydroxide 0.08kg mixing, is crossed 300 mesh sieves, gets the powder of calcium hydroxide and zinc hydroxide mixture; By mass ratio is 0.5: 1 mixed ethanol and glycerol, makes 12kg ethanol glycerol mixed liquor; Described powder is added in the ethanol glycerol mixed liquor, evenly make the A component in stirring at room;
Second step added concentrated phosphoric acid in the ethanol, stirred and made the B component, and wherein phosphoric acid and alcoholic acid mass ratio are 1: 6;
The 3rd step, with the A component pack into take back stream device the 25L reactor in, stirring is warming up to little boiling, after 20 minutes, first quick and back slow add in reactor by 2～10ml/min the B component, the pH of mixed value stabilization stopped at 8.3 o'clock adding in the question response still, continued reaction 3 hours, and course of reaction keeps little and boils and stir;
In the 4th step, with the suction distillation column while hot of the mixed liquor in the described reactor, normal pressure control tower top temperature down is 78 ℃ and distills, and stops during for 0.47wt% up to the bottoms ethanol content, and the discharging cooling promptly gets nano-hydroxyapatite glycerin cement.
The nano-hydroxyapatite glycerin cement that makes is made toothpaste by known toothpaste production technology, and the raw material that wherein prepares toothpaste is made of by mass percent following material: nano-hydroxyapatite glycerin cement 28, CMC1.2, K
122.0, CaCO
345, tetrasodium pyrophosphate 1.0, saccharin sodium 0.2, essence 1.0, distilled water 21.6.After measured, containing zinc doping nanometer hydroxyapatite content in the toothpaste that makes is that 4.3wt%, calcium glycerophosphate are about 0.2wt%.
The first step with pulverizing after calcium oxide 0.85kg and the eight water Strontium hydrate. 0.15kg mixing, is crossed 300 mesh sieves, gets the powder of calcium oxide and eight water Strontium hydrate. mixture; By mass ratio is 0.1: 1 mixed ethanol and glycerol, makes 12kg ethanol glycerol mixed liquor; Described powder is added in the ethanol glycerol mixed liquor, evenly make the A component in stirring at room;
Second step added concentrated phosphoric acid in the ethanol, stirred and made the B component, and wherein phosphoric acid and alcoholic acid mass ratio are 1: 2;
The 3rd step, with the A component pack into take back stream device the 25L reactor in, stirring is warming up to little boiling, after 30 minutes, first quick and back slow add in reactor by 2～10ml/min the B component, the pH of mixed value stabilization stopped at 8.5 o'clock adding in the question response still, continued reaction 6 hours, and course of reaction keeps little and boils and stir;
In the 4th step, with the suction distillation column while hot of the mixed liquor in the described reactor, normal pressure control tower top temperature down is 78 ℃ and distills, and stops during for 0.48wt% up to the bottoms ethanol content, and the discharging cooling promptly gets nano-hydroxyapatite glycerin cement.
The nano-hydroxyapatite glycerin cement that makes is made toothpaste by known toothpaste production technology, and the raw material that wherein prepares toothpaste is made of by mass percent following material: nano-hydroxyapatite glycerin cement 30, CMC1.0, K
121.7, CaHPO
445, saccharin sodium 0.2, essence 1.0, distilled water 21.1.After measured, containing strontium doping nanometer hydroxyapatite content in the toothpaste that makes is that 4.5wt%, calcium glycerophosphate are about 0.3wt%.
Embodiment 7
The first step with pulverizing after calcium oxide 0.60kg and the strontium oxide 0.08kg mixing, is crossed 300 mesh sieves, gets the powder of calcium oxide and strontium oxide mixture; By mass ratio is 1.2: 1 mixed ethanol and glycerol, makes 12kg ethanol glycerol mixed liquor; Described powder is added in the ethanol glycerol mixed liquor, evenly make the A component in stirring at room;
Second step added concentrated phosphoric acid in the ethanol, stirred and made the B component, and wherein phosphoric acid and alcoholic acid mass ratio are 1: 10;
The 3rd step, with the A component pack into take back stream device the 25L reactor in, stirring is warming up to little boiling, after 30 minutes, first quick and back slow add in reactor by 2～10ml/min the B component, the pH of mixed value stabilization stopped at 8.5 o'clock adding in the question response still, continued reaction 4 hours, and course of reaction keeps little and boils and stir;
The 4th step with the suction distillation column while hot of the mixed liquor in the described reactor, stopped during for 0.48wt% up to the bottoms ethanol content under the distilling under reduced pressure, and the discharging cooling obtains nano-hydroxyapatite glycerin cement.
The nano-hydroxyapatite glycerin cement that makes is made toothpaste by known toothpaste production technology, and the raw material that wherein prepares toothpaste is made of by mass percent following material: nano-hydroxyapatite glycerin cement 28, CMC1.2, K
122.0, CaCO
345, tetrasodium pyrophosphate 1.0, saccharin sodium 0.2, essence 1.0, distilled water 21.6.After measured, containing strontium doping nanometer hydroxyapatite content in the toothpaste that makes is that 6.0wt%, calcium glycerophosphate are about 0.2wt%.
Embodiment 8
The first step with pulverizing after calcium oxide 0.65kg and the magnesium oxide 0.1kg mixing, is crossed 300 mesh sieves, gets the powder of calcium oxide and magnesia mixture; By mass ratio is 1: 1 mixed ethanol and glycerol, makes 12kg ethanol glycerol mixed liquor; Described powder is added in the ethanol glycerol mixed liquor, evenly make the A component in stirring at room;
Second step added concentrated phosphoric acid in the ethanol, stirred and made the B component, and wherein phosphoric acid and alcoholic acid mass ratio are 1: 10;
The 3rd step, with the A component pack into take back stream device the 25L reactor in, stirring is warming up to little boiling, after 30 minutes, first quick and back slow add in reactor by 2～10ml/min the B component, the pH of mixed value stabilization stopped at 8.5 o'clock adding in the question response still, continued reaction 4 hours, and course of reaction keeps little and boils and stir;
In the 4th step, with the suction distillation column while hot of the mixed liquor in the described reactor, distilling under reduced pressure stops during for 0.45wt% up to the bottoms ethanol content, and the discharging cooling obtains nano-hydroxyapatite glycerin cement.
The nano-hydroxyapatite glycerin cement that makes is made toothpaste by known toothpaste production technology, and the raw material that wherein prepares toothpaste is made of by mass percent following material: nano-hydroxyapatite glycerin cement 28, CMC1.2, K
122.0, CaCO
345, tetrasodium pyrophosphate 1.0, saccharin sodium 0.2, essence 1.0, distilled water 21.6.After measured, containing the nano hydroxylapatite doped content of magnesium in the toothpaste that makes is that 6.0wt%, calcium glycerophosphate are about 0.2wt%.
Embodiment 9
The first step with pulverizing after calcium oxide 1.23kg and the zinc oxide 0.89kg mixing, is crossed 300 mesh sieves, gets the powder of calcium oxide and zinc oxide mixture; By mass ratio is 0.5: 1 mixed ethanol and glycerol, makes 12kg ethanol glycerol mixed liquor; Described powder is added in the ethanol glycerol mixed liquor, evenly make the A component in stirring at room;
Second step was 1: 1 mixed glycerol and an ethanol by mass ratio, the glycerol alcohol mixeding liquid; Concentrated phosphoric acid is added in the ethanol, stir and make the B component, wherein the mass ratio of phosphoric acid and glycerol alcohol mixeding liquid is 1: 10;
The 3rd step, with the A component pack into take back stream device the 25L reactor in, stirring is warming up to little boiling, after 30 minutes, first quick and back slow add in reactor by 2～20ml/min the B component, the pH of mixed value stabilization stopped at 8.5 o'clock adding in the question response still, continued reaction 4 hours, and course of reaction keeps little and boils and stir;
In the 4th step, with the suction distillation column while hot of the mixed liquor in the described reactor, distilling under reduced pressure stops during for 0.45wt% up to the bottoms ethanol content, and the discharging cooling promptly gets nano-hydroxyapatite glycerin cement.
The nano-hydroxyapatite glycerin cement that makes is made toothpaste by known toothpaste production technology, and the raw material that wherein prepares toothpaste is made of by mass percent following material: nano-hydroxyapatite glycerin cement 28, CMC1.2, K
122.0, CaCO
345, tetrasodium pyrophosphate 1.0, saccharin sodium 0.2, essence 1.0, distilled water 21.6.After measured, containing zinc doping nanometer hydroxyapatite content in the toothpaste that makes is that 5.9wt%, calcium glycerophosphate are about 0.3wt%.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1, a kind of preparation method of nano-hydroxyapatite glycerin cement is characterized in that, comprises the steps:
The first step is pulverized calcium preparation, crosses 300 mesh sieves, gets the calcium preparation powder; By mass ratio is 0.1～1.5: 1 mixed ethanol and glycerol, ethanol glycerol mixed liquor; Add described calcium preparation powder in ethanol glycerol mixed liquor, stir and make the A component, wherein the content of calcium preparation is 1～20wt% in the A component;
Second step was 0～1: 1 mixed glycerol and ethanol by mass ratio, the glycerol alcohol mixeding liquid; With mass percent concentration is that 85% concentrated phosphoric acid adds in the glycerol alcohol mixeding liquid, stirs and makes the B component, and wherein the mass ratio of phosphoric acid and glycerol alcohol mixeding liquid is 1: 2～10;
The 3rd step, the A component is packed in the reactor, stir and be warming up to little boiling, after 20～30 minutes, the B component is slowly joined in the reactor, the pH value of mixed liquor is stabilized at 8～8.5 o'clock and stops to add the B component in reactor, and little boiling continued reaction 3～6 hours down;
The 4th step in the mixed liquor suction distilling apparatus in the described reactor, was distilled to ethanol content≤0.5wt%, got nano-hydroxyapatite glycerin cement.
According to the preparation method of the described nano-hydroxyapatite glycerin cement of claim 1, it is characterized in that 2, the calcium preparation in the described first step is calcium oxide or calcium hydroxide.
According to the preparation method of the described nano-hydroxyapatite glycerin cement of claim 1, it is characterized in that 3, the calcium preparation in the described first step is the mixture of a kind of and calcium oxide or calcium hydroxide in the oxide of the oxide of oxide, zinc of strontium and magnesium; In the mixture, the mol ratio of strontium, zinc or magnesium and calcium is 0.02～0.5: 1.
According to the preparation method of the described nano-hydroxyapatite glycerin cement of claim 1, it is characterized in that 4, the calcium preparation in the described first step is the mixture of a kind of and calcium oxide or calcium hydroxide in the hydroxide of the hydroxide of hydroxide, zinc of strontium and magnesium; In the mixture, the mol ratio of strontium, zinc or magnesium and calcium is 0.02～0.5: 1.
5, according to the preparation method of the described nano-hydroxyapatite glycerin cement of claim 1, it is characterized in that, in the described first step is 0.5～1: 1 mixed ethanol and glycerol by mass ratio, and the content of calcium preparation is 5～15wt% in the A component.
According to the preparation method of the described nano-hydroxyapatite glycerin cement of claim 1, it is characterized in that 6, the distilling apparatus in described the 4th step is a distillation column; Described distillation refers to air-distillation or distilling under reduced pressure.
According to the preparation method of the described nano-hydroxyapatite glycerin cement of claim 6, it is characterized in that 7, tower top temperature is 78～78.5 ℃ during described air-distillation.
8, the nano-hydroxyapatite glycerin cement that makes of the preparation method of the described nano-hydroxyapatite glycerin cement of a kind of claim 1 comprises that particle diameter is nanometer hydroxyapatite particle, calcium glycerophosphate, the G ﹠ W of 20～50nm.
9, the described nano-hydroxyapatite glycerin cement of claim 8 is as the application of the glycerin component in the toothpaste.
According to the application of the described nano-hydroxyapatite glycerin cement of claim 9 in toothpaste, it is characterized in that 10, the nanometer hydroxyapatite that joins in the toothpaste accounts for 2～6% of toothpaste gross mass; The calcium glycerophosphate that adds in the toothpaste accounts for 0.05～1.5% of toothpaste gross mass.
Priority Applications (1)
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| CN2008100302453A CN101342115B (en) | 2008-08-19 | 2008-08-19 | Nano-hydroxyapatite glycerin cement, preparation method and application in toothpaste thereof |
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| CN2008100302453A CN101342115B (en) | 2008-08-19 | 2008-08-19 | Nano-hydroxyapatite glycerin cement, preparation method and application in toothpaste thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804144A (en) * | 2014-01-16 | 2014-05-21 | 东南大学 | Method for homogeneously synthesizing glycerol calcium |
| CN107049828A (en) * | 2017-06-22 | 2017-08-18 | 缪来耿 | A kind of anti-caries toothpaste and preparation method thereof |
| CN109568189A (en) * | 2018-12-27 | 2019-04-05 | 温州市森马网络技术有限公司 | One kind is antibacterial to remove stain nanometer toothpaste and preparation method thereof |
| CN113526478A (en) * | 2021-07-14 | 2021-10-22 | 上海市第十人民医院 | Glycerol-stabilized nano calcium phosphate ion cluster material, preparation method and application |
-
2008
- 2008-08-19 CN CN2008100302453A patent/CN101342115B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804144A (en) * | 2014-01-16 | 2014-05-21 | 东南大学 | Method for homogeneously synthesizing glycerol calcium |
| CN103804144B (en) * | 2014-01-16 | 2015-10-28 | 东南大学 | A kind of method of Homogeneous synthesis glycerine calcium |
| CN107049828A (en) * | 2017-06-22 | 2017-08-18 | 缪来耿 | A kind of anti-caries toothpaste and preparation method thereof |
| CN109568189A (en) * | 2018-12-27 | 2019-04-05 | 温州市森马网络技术有限公司 | One kind is antibacterial to remove stain nanometer toothpaste and preparation method thereof |
| CN113526478A (en) * | 2021-07-14 | 2021-10-22 | 上海市第十人民医院 | Glycerol-stabilized nano calcium phosphate ion cluster material, preparation method and application |
| CN113526478B (en) * | 2021-07-14 | 2023-09-12 | 上海市第十人民医院 | Glycerol-stable nano calcium phosphate ion cluster material, preparation method and application |
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|---|---|
| CN101342115B (en) | 2010-11-10 |
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