CN103159197A - Method for preparing silver-containing calcium phosphate - Google Patents
Method for preparing silver-containing calcium phosphate Download PDFInfo
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- CN103159197A CN103159197A CN2013101212563A CN201310121256A CN103159197A CN 103159197 A CN103159197 A CN 103159197A CN 2013101212563 A CN2013101212563 A CN 2013101212563A CN 201310121256 A CN201310121256 A CN 201310121256A CN 103159197 A CN103159197 A CN 103159197A
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- calcium phosphate
- argentiferous
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- clear liquid
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- 239000001506 calcium phosphate Substances 0.000 title claims abstract description 93
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 title claims abstract description 92
- 229910000389 calcium phosphate Inorganic materials 0.000 title claims abstract description 91
- 235000011010 calcium phosphates Nutrition 0.000 title claims abstract description 91
- 239000004332 silver Substances 0.000 title claims abstract description 38
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 33
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 76
- 239000000843 powder Substances 0.000 claims abstract description 47
- 238000002360 preparation method Methods 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 14
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- 230000010354 integration Effects 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 7
- 230000018044 dehydration Effects 0.000 claims abstract description 3
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- -1 polyoxyethylene Polymers 0.000 claims description 30
- 239000011575 calcium Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 20
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 18
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 239000013081 microcrystal Substances 0.000 claims description 11
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910001424 calcium ion Inorganic materials 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 230000004907 flux Effects 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 2
- 238000000352 supercritical drying Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 14
- 238000012546 transfer Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 9
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[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 XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 9
- 230000007704 transition Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 8
- 230000003993 interaction Effects 0.000 description 8
- 239000003446 ligand Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 230000000536 complexating effect Effects 0.000 description 6
- 229920002521 macromolecule Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000002421 anti-septic effect Effects 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052587 fluorapatite Inorganic materials 0.000 description 2
- 229940077441 fluorapatite Drugs 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000002105 nanoparticle 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 229940078499 tricalcium phosphate Drugs 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- UXCIYSZDIOQTQG-UHFFFAOYSA-K calcium;silver;phosphate Chemical compound [Ca+2].[Ag+].[O-]P([O-])([O-])=O UXCIYSZDIOQTQG-UHFFFAOYSA-K 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 210000003793 centrosome Anatomy 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000005182 potential energy surface Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003578 releasing effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- DTPQZKZONQKKSU-UHFFFAOYSA-N silver azanide silver Chemical compound [NH2-].[Ag].[Ag].[Ag+] DTPQZKZONQKKSU-UHFFFAOYSA-N 0.000 description 1
- 229940019931 silver phosphate Drugs 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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Abstract
The invention discloses a method for preparing silver-containing calcium phosphate and relates to silver-containing calcium phosphate. The method for preparing silver-containing calcium phosphate, disclosed by the invention, is based on a differential reaction technology and has the advantages that the continuous and stable production can be achieved, the process preparation and raw materials are simple, the reaction conditions are mild and controllable, the production cycle is short, and the whiteness is stable. The method comprises the following steps of: (1) preparing raw material liquid; (2) conveying A-phase clear liquid and B-phase clear liquid, which are obtained in the step (1), to a micro-channel continuous mixing system through a pipeline by a metering pump of a raw material conveying system, and carrying out continuous integration reaction so as to form silver-containing calcium phosphate aggregate; (3) conveying a mixing reaction product, namely silver-containing calcium phosphate aggregate sol, to a dehydration and washing device, and drying the washed product so as to obtain amorphous silver-containing calcium phosphate powder; and (4) carrying out high temperature treatment on the amorphous silver-containing calcium phosphate powder obtained in the step (3), thereby obtaining silver-containing calcium phosphate microcrystalline powder with stable whiteness.
Description
Technical field
The present invention relates to argentiferous calcium phosphate, especially utilize the method for transition state complexes preparation argentiferous calcium phosphate.
Background technology
In recent years, along with the progressively raising of national life level, because people have higher requirement to life comfort level and health level, so silver-based inorganic antibacterial agent obtained widely research, and is used widely in fields such as weaving, building materials, environmental protection.Because most antibacterial facility can occur contact frequently with human body, thus to its anti-biotic material that uses except require anti-microbial property well, also should have good toxicological harmless and biocompatibility.Calcium phosphate is the material that a class has good biocompatibility, and present studies show that, silver and calcium phosphate is compound, as a kind of broad-spectrum inorganic antibiotic agent, have safe, not volatile, be difficult for to decompose, good heat resistance, harmless and can long acting antibiotic etc. characteristics.
Chinese patent 02129370.8 discloses a kind of silver-carried fluor apatite antimicrobials and preparation method thereof, at first the method prepares amorphous nano silver-carrying fluorapatite powder with coprecipitation method, and then strengthen its year of silver-colored effect by high-temperature calcination, this method adopts the intermittent type flow process, is not easy to industrialization and produces continuously.
Chinese patent 02134722.0 discloses a kind of delay-released inorganic nano antiseptic with high whiteness and preparation method thereof, its preparation method comprises that the ca nitrate soln that will contain antibacterial metal salts is added drop-wise to the pH value and generates hydroxyapatite for reaction in the phosphate solution of 11-12, ageing, with water rinse precipitation and filtration, oven dry, pulverize high-temperature calcination, superfine grinding etc.Owing to adopting ammoniacal liquor to regulate the pH value, therefore can form silver ammonia complex, make the amount of being written into of silver in final product descend, affect the yield of product; This patent only considers that Ca/P is 1.67 synthetic system in addition, and in fact Ca/P will have the room generation of more calcium less than 1.67 o'clock, make more silver be loaded into the room.
Chinese patent 02134716.6 discloses a kind of needle inorganic nano antiseptic with great length-diameter ratio and preparation method thereof, its preparation method comprises that the ca nitrate soln that will contain antibacterial metal salts splashes in the phosphate solution that contains the dispersion agent dimethyl formamide, reaction generates hydroxyapatite, water and ethanol rinsing, supersound process adds antibacterial metal ions, washing, filter, calcining is pulverized etc.Weak point is the silver ammonia complex that forms, and reduces the rate that is written into of silver ions, and ratio of calcium and phosphorus 1.67 in addition, does not have enough calcium room also can reduce the amount of being written into of silver.
Chinese patent 200810103452.7 discloses a kind of manufacture method of argentum-carried hydroxylapatite and as the application of antiseptic-germicide, pass through infusion method, hydroxyapatite is joined in the mixing solutions of Silver Nitrate and cerous nitrate and react, wherein the concentration of Silver Nitrate and cerous nitrate is 0.01mol/L～0.2mol/L, temperature of reaction is 30～60 ℃, and the reaction times is 2～5 hours; Precipitation, suction filtration, oven dry, grinding obtain the antiseptic-germicide powder.The less stable of the antibiotic ion in this its structure of class antiseptic-germicide is written into ratio low, and color is unstable, and illumination is easy to change, and the burst size in early stage of antiseptic-germicide ion is large, actually can't reach long-term releasing effect.
Studies show that of microminiaturized multiplexer spare, in the differential reactive system, due to the characteristic dimension of passage at micron order, along with reducing of yardstick, thermograde, pressure gradient, concentration gradient and density gradient etc. increase very soon, to cause the increase of mass transfer, driving force of heat transfer, thereby shorten diffusion length, enlarge the diffusion flux of unit volume or unit surface.The conventional interchanger of ratio of heat transfer coefficient is large more than 10 times, and mixing time may diminish to even microsecond magnitude of millisecond, makes transformation efficiency, controllability and the conversion rate of reaction obviously improve.
Microreactor has the unrivaled superiority of conventional apparatus:
1, little, the quality of equipment requisite space and consuming little energy and corresponding time short, improved the security of equipment and the controllability of reaction process.
What 2, the differential reaction technology was mainly strengthened is transmission characteristic, and linear content is contracted to micron order, the contact gear ratio surface-area increases and volume reduces, and is to the reinforcement of quality and heat transfer process and the improvement of fluid-flow mode.
3, throughput is amplified easily, and the differential conversion unit replaces device geometry to amplify by number amplification flexibly, guarantees that the essential property of each parallel units is consistent, realizes stably producing of product.
4, but the achievement in research rapid conversion is productivity, and low cost realizes industrialization and mass-producing.
Polymer-metal complex (MMC) is must be obligato to tellurian life, polymer and by a ligand moiety around metal between ad hoc structure arrange the activity and selectivity greatly affect MMC." polymer " singly do not refer to organic polymer, comprises inorganic compounds of high molecular weight yet.Metal can be metal ion, metal complex, metallo-chelate or metal cluster.Polymer and metallographic phase produce the product with new Static and dynamic characteristic in conjunction with unlimited structure possibility is provided; On the other hand, MMC also causes electronics, proton and micromolecular interaction.MMC can be divided into following three kinds:
The I type is bonded to metal complex on polymer carrier by part and metal ion.
The II type is as the metal complex of polymer chain or network components.
The metal complex that the III type is connected with macromolecular compound with physical action.
In MMC, the chemical reactivity at complexing position and physicochemical property are subject to complexing position and the very large impact of polymer environmental interaction.In MMC, complexing position and the interaction around the polymeric matrix around it affect physicochemical property and the chemical reaction at complexing position consumingly.Interaction in MMC is mainly various weak bonding forces, for example, and coordinate bond, hydrogen bond, charge transfer interaction, hydrophobic interaction etc.These interactions have multiple and dynamic character, co-action in MMC.In MMC, the electronic transfer process at complexing position usually is subject to the impact of the dynamic conformational change of molecule environment on every side of complexing position.In MMC, interactional feature shows as: the binding equilibrium attitude, coordination replaces, multielectron transfer process, molecule aggregates, molecular conversion etc.The molecule environment is controlled arranging and movability of electronics.
Present research quantitative description GOLD FROM PLATING SOLUTION belongs to the equilibrium state of ion and macromolecule ligand formation complex compound:
In formula, [M
z+] be the concentration (mol/L) of equilibrium state metal ion, [L
-] and [ML
n (z-n)+] be corresponding part and the concentration (mol/L) that forms complex compound,
The total rate constant that forms complex compound,
The part mean number of being combined with each metal ion.
The thermodynamics situation not only be subject to high molecular conformation in reaction process, chain flexible and the impact that changes of electrically charged these several respects, and be subject to the impact of original material and reaction product Energy value.Thermodynamic behaviour can estimate by temperature relation, namely
For the Gibbs free energy,
Maximum contribution is usually from entropy item △ S, and enthalpy item △ H is usually constant.When calculating thermodynamical coordinate, (interior coordination joint, CNd is by isolated functional group and the MX of macromolecule ligand to form parameter for the coordination joint
nForm) and chain change parameter all should take in.The variation of free energy is relevant to the change of macromolecular chain mobility, and the free energy item addition with all has:
△G=△G
CNd+△G
MMC
When usually forming MMC, free energy reduces, and this is conducive to the formation of MMC from thermodynamic (al) viewpoint.So-called polymkeric substance chelate effect (playing the free energy change that produces in the environment of stabilization because metal derivative is added on macromolecule ligand or to it) further is enhanced due to some new factors.Because the formation of MMC can change high molecular part, molecule and supramolecular structure, this comprises adjustment and other changes of complexation constant, synergistic effect, structural arrangement.
MX
nMay form MMC on the different positions of polymer chain with macromolecule ligand, if q MX
nMolecular linkage is on the polymer chain that contains the individual active coordination of p position, and the number of the complex compound that may form is Cpq.MX
nCan be bonded on single chain or on several macromolecular chain.MX
nThe process of addition not only has chemical interaction, and is accompanied by the change of local links's mobility.MX
nThe bonding that occurs in addition process causes the reactive raising of macromolecule ligand:
Complex compound forms constant and can be expressed as:
σ=k
i/k
i-1
In formula, σ is the coordination factor, forms the increase of constant between the continuous two steps reaction of its expression.Because main entropy change occurs in the first step MX
nIn the process of addition, so supposition all formation constants except the first step are all close.All later processes of the first step all can be considered the formation of ring in molecule.
The Nomenclature Composition and Structure of Complexes of polymer-metal complex not only is subject to the impact of metal (M) and ligand (L) kind, but also is subject to the impact of specific polymer parameter (for example degree of crosslinking, the distribution of L) and part profile.The complex compound forming process is attended by many complicated factors, such as impact of ion-exchange equilibrium, part conformational change, electrostatic surface potential change etc.Between central ion in MMC (atom) and ligand by the coordinate bond combination.The hydridization unoccupied orbital that the empty virtual orbital of central ion or electron rearrangement produce is accepted and shares part to provide lone-pair electron to form coordinate bond.Participate in into the geometric configuration of type decided title complex of empty virtual orbital of the central ion of key, for example hybridized orbital is that the part thing of sp is linear, and hybridized orbital is sp
2Title complex be plane triangle, the rail track is sp
3Title complex be positive tetrahedron, hybridized orbital is dsp
2Title complex be plane square, hybridized orbital is d
2sp
3, sp
3d
2Title complex be octahedra.
Summary of the invention
The object of the invention is to provides based on the differential reaction technology in order to overcome existing argentiferous calcium phosphate preparation method's deficiency, but the serialization stably manufactured, the technique raw materials is simple, the reaction conditions gentleness is controlled, and is with short production cycle, the preparation method of a kind of argentiferous calcium phosphate that whiteness is stable.
Concrete steps of the present invention are as follows:
1) stock liquid preparation: with Ca
2+Ion source, PO
4 3-Ion source, Ag
+Ion source, 5 kinds of preparation of raw material of basic cpd and polyoxyethylene glycol become A phase clear liquid and B clear liquid mutually, take water as solvent adjustment A phase clear liquid with the B concentration of clear liquid mutually, with A phase clear liquid and B mutually clear liquid be contained in respectively in two head tanks; Described A phase clear liquid is that at least a kind of preparation of raw material in above-mentioned 5 kinds of raw materials forms, and described B phase clear liquid is that at least a kind of preparation of raw material in above-mentioned 5 kinds of raw materials forms; Described A phase clear liquid and the B final raw material of clear liquid preparation mutually always plant number and must all contain above-mentioned 5 kinds of raw materials;
2) volume pump by source material delivery system by the road with the A phase clear liquid in step 1) and B mutually clear liquid be delivered to the microchannel continuous mixing system, the reaction of serialization integration forms argentiferous calcium phosphate aggregate; The molar ratio of material of whole system: (F
A* C
A-Ca+ F
B* C
B-Ca+ F
A* C
A-Ag+ F
B* C
B-Ag)/(F
A* C
A-P+ F
B* C
B-P)=1.0～2.0, two-phase total flux: F
A+ F
B=10～5000mL/min, in formula, F
ABe the A phase flow rate, unit is mL/min; F
BBe the B phase flow rate, unit is mL/min; C
A-CaFor A mutually in Ca
2+Ionogenic concentration, unit is M; C
B-CaFor B mutually in Ca
2+Ionogenic concentration, unit is M; C
A-AgFor A mutually in Ag
+Ionogenic concentration, unit is M; C
B-AgFor B mutually in Ag
+Ionogenic concentration, unit is M; C
A-PFor A mutually in PO
4 3-Ionogenic concentration, unit is M; C
B-PFor B mutually in PO
4 3-Ionogenic concentration, unit is M;
3) reaction product mixture argentiferous calcium phosphate aggregate colloidal sol is transported to the dehydration washing device, the product after washing is carried out drying, obtain non-crystalline state argentiferous calcium phosphate powder;
4) with step 3) gained non-crystalline state argentiferous calcium phosphate powder through pyroprocessing, obtain the stable argentiferous calcium phosphate microcrystal powder of whiteness.
In step 1), described Ca
2+Ionogenic concentration C
CaCan be 0.01～5M; PO
4 3-Ionogenic concentration C
PCan be 0.01～5M; Described Ag
+Ion source can be selected from Silver Nitrate, and the mol ratio of the add-on of silver ions and the add-on of calcium ion can be 0.001～0.2; The mol ratio of the add-on of described polyoxyethylene glycol and the add-on of calcium ion can be 0.1～10, and with the structural unit calculating mole number of polyoxyethylene glycol, the molecular weight of polyoxyethylene glycol can be 1500～20000; Described basic cpd includes but not limited to sodium hydroxide or potassium hydroxide, and the concentration of basic cpd can be 0.01～15M; The temperature of described preparation of raw material process can be 15～50 ℃; Described A phase clear liquid or B phase clear liquid are the transition state complex compound, require to place not occur at least 1 month precipitating or suspended substance.
In step 2) in, described volume pump by source material delivery system with the A phase clear liquid in step 1) and B mutually clear liquid be delivered to the microchannel continuous mixing system can be under 15～50 ℃ of envrionment conditionss by source material delivery system volume pump with the A phase clear liquid in step 1) and B mutually clear liquid steadily be delivered to the microchannel continuous mixing system simultaneously, make each fluid components by evenly differential injection, realize mass-and heat-transfer equably on microscopic scale, enhancing mixed kinetics, the reaction of serialization integration forms argentiferous calcium phosphate aggregate; The size of described microchannel can be 10～200 μ m; The flow reproducibility error of described volume pump can≤1%, pressure range can be 14.5～1450psi, pressure pulse can≤29psi; The material of described pipeline can adopt 316 stainless steels, 316L stainless steel or meet the stainless steel tube of ASTM A269 or equivalent standard, and internal diameter is 1/16～1 inch, operating pressure 〉=6000psi.
In step 3), described drying can adopt conventional oven dry, lyophilize, spraying drying, supercritical drying or vacuum-drying etc.
In step 4), the temperature of described pyroprocessing can be 500～1300 ℃, and the atmosphere of processing can be air, and the time of processing can be 0.5～10h; With non-crystalline state argentiferous calcium phosphate powder through pyroprocessing, make silver ions more stable in crystalline network, thereby obtain the stable argentiferous calcium phosphate microcrystal powder of whiteness, and the release uniformly from lattice that silver ions is continued, reach the long acting antibiotic ability.
Traditional stirred autoclave mostly is intermittent process, is difficult to avoid local solubility to occur too high, causes the mass-and heat-transfer inequality to have, the transformation efficiency of impact reaction and the consistence of quality.Little hybrid reaction technology is the stable key of reappearing of product, be compared to traditional stirred autoclave, has overcome product exists purity, pattern, size and distribution between different batches difference.
The little mixing flow reactor that the present invention relates to is the little mixed structure of a kind of multilayer (Multilamination), dispersed phase fluid is by evenly differential injection, fluid constantly separates repolymerization, physique by micro mixing-reactor becomes n thin layer with fluid well-distributing differential to be mixed, and make its mutual contact, according to the Fick law, will be reduced to diffusion time: t～d
2/ (n
2* D) in formula, t is mixing time; The little diffusion characteristic yardstick of d; N is thin layer quantity; D is spread coefficient.
In the time of in fluid to be mixed is in same microchannel, along with reducing of yardstick, thermograde, pressure gradient, concentration gradient and density gradient etc. increase very soon, to cause the increase of mass transfer, driving force of heat transfer, thereby shorten the molecular diffusion distance, enlarged the diffusion flux of unit volume or unit surface.Therefore rely on molecular diffusion just can (millisecond is to Microsecond grade) realize evenly mixing completing chemical reaction within the extremely short time, make transformation efficiency, controllability and the conversion rate of reaction obviously improve, reach the effect that micromixing does not have.
Chemical reaction is to rearrange combination between atom from seeing in essence, and in this process, the potential energy of system reduces, and the reaction that makes can go on.Need from the reactant to the product through a transition state, in this transition state, reactant part scission of link, product part Cheng Jian is referred to as the transition state complex compound, and its energy is the extreme point on potential energy surface, and its energy difference with reactant is to react the potential barrier that must overcome.Chemical reaction is not just can complete by the simple collision of reactant molecule, but at reactant in the process of resultant, passed through the transition state of a higher-energy.Reaction model is as follows:
Polyoxyethylene glycol (PEG) is formed by ethylene oxide polymerization, and molecular formula is HO (CH
2CH
2O)
nH only has two kinds of hydrophilic groups of hydroxyl and ether and without hydrophobic group.As a kind of protonic solvent, nontoxic, nonirritant has good water-solublely, and excellent stability is not subject to ionogen and acid, alkali impact.And with many organic matter components, good intermiscibility is arranged.They have good oilness, moisture retention, dispersiveness, caking agent, static inhibitor and softening agent etc., all have very widely in the industries such as makeup, pharmacy, chemical fibre, rubber, plastics, papermaking, paint, plating, agricultural chemicals, metal processing biotechnology and food-processing and use.
In the system of calcium, silver metal ion, infrared result shows that the absorption peak of C-O-C key obviously drifts about to lower wave number, be because the C-O-C key has been subject in the environment different groups (or ion) to its different impact in this interval asymmetrical stretching vibration, its vibrational frequency is reduced.Infer thus calcium ion to the sucking action of positro cloud in the C-O-C group, cause the σ key share electron pair of oxygen and other two carbon atoms more to be partial to oxygen, cause that absorption peak is offset to lower wave number.When forming title complex, at first the unoccupied orbital that centrosome provides must carry out hydridization, the new hybridized orbital that equates with the ligating atom number that forming energy is identical.The sp of calcium ion
3d
2The sp hybridized orbital of hybridized orbital and silver ions provides a plurality of unoccupied orbitals, simultaneously, and owing to being all sp with ether group Sauerstoffatom and the Sauerstoffatom in terminal hydroxy group of two methylene radical bondings in PEG
3Hydridization, wherein two single electron tracks form the σ key with adjacent C or H respectively, also have in addition two hybridized orbitals with lone-pair electron not become key, can be by calcium ion out-shell electron configuration sp
3d
2Unoccupied orbital in the sp hybridized orbital of hybridized orbital and silver ions is accepted in PEG the lone-pair electron that share on oxygen, and the Sauerstoffatom in PEG has lone-pair electron and often shows as the electric charge donor, so Ca
2+, Ag
+Can form coordinate bond with C-O-C.
The present invention is by introducing polyoxyethylene glycol as the complex compound medium, make being present in the transition state complex compound that calcium and silver metal ion can be stable, reduced on the one hand the energy barrier of reaction formation final product, improve the utilization ratio of silver ions, solved the low problem that is difficult to improve of argentiferous calcium phosphate silver content; On the other hand; in PEG, hydrophilic Sauerstoffatom is pulled out the outside that is in chain by water molecules; in building-up process can so that an end of polymer long-chain tightly be adsorbed in calcium phosphate micelle surface; thereby form one deck polymer protective film; so when close to each other with the particle of same sex electric charge; electrostatic repulsion is added the space steric effect of polymer protective film, makes the magnetism between nano particle weakened, has effectively suppressed the reunion of nanoparticle.
The present invention makes Ca in the transition state complex compound system that contains the polyoxyethylene glycol formation
2+Ion, PO
4 3-Ion and Ag
+Solion is realized the differential contact combination reaction of each fluid components by the continuous mixing reactor in microchannel, mass transfer and heat transfer process in consolidation system, form fast argentiferous calcium phosphate aggregate colloidal sol, through separating, washing, drying obtains non-crystalline state argentiferous calcium phosphate powder, obtain the stable crystallite attitude argentiferous calcium phosphate powder of whiteness through pyroprocessing again
The present invention has following outstanding advantages:
1) in pressed powder, silver content significantly improves, this is because argentiferous calcium phosphate aggregate colloidal sol internal structure can well be stablized silver content, make in final argentiferous calcium phosphate powder the silver content scope at 0.1～10wt%, have remarkable lifting compared to the 5.5wt% silver content of argentum-carried hydroxylapatite in the past;
2) because creativeness is introduced the transition state complex compound, therefore can realize that under normal temperature or comparatively high temps, the stable of (15～50 ℃) non-crystalline state argentiferous calcium phosphate powder synthesizes, solved the difficult problem that non-crystalline state argentiferous calcium phosphate is difficult to synthesize at this temperature in the past, reduce simultaneously energy consumption cost, be easy to realize the stabilization of industry mass production;
3) the argentiferous calcium phosphate microcrystal powder after pyroprocessing of the present invention, whiteness is stable, has overcome the problem easy to change of carrying silver-colored calcium phosphate powder that ion exchange method obtains of soaking;
4) product quality stable homogeneous, wherein one of reason hybrid reaction process adopts the continuous mixing reactor in microchannel, and each fluid components is carried out the differential refinement, has greatly shortened the molecular diffusion distance, realize mass-and heat-transfer equably on microscopic scale, enhancing mixed kinetics;
5) preparation technology's flow process of the present invention's employing is simple, and a step serialization is synthetic, and process is accurately controlled, and can realize stably producing of product.
Description of drawings
Fig. 1 is for to carry out X-ray powder diffraction (XRD) analytical results to dried powder.In Fig. 1, X-coordinate be diffraction angle (°), ordinate zou is relative intensity (a.u.).
Fig. 2 is that the selected diffraction (SAED) by transmission electron microscope is analyzed.In Fig. 2, scale is 51nm.
Fig. 3 carries out composition analysis in conjunction with energy dispersion X-ray spectrum (EDS).In Fig. 3, X-coordinate is energy (keV).
Fig. 4 is the XRD analysis result of non-crystalline state argentiferous calcium phosphate after 950 ℃ of processing.In Fig. 4, X-coordinate be diffraction angle (°), ordinate zou is relative intensity (a.u.); Mark
For bata-tricalcium phosphate (β-TCP), ◆ be hydroxyapatite (HA).
Embodiment
1.A the preparation of phase stock liquid contains the nitrocalcite of 0.09M, the Silver Nitrate of 0.002M and polyoxyethylene glycol (PEG-20000) solution of 0.3M;
2.B the preparation of phase stock liquid contains the phosphoric acid of 0.06M and the sodium hydroxide solution of 0.18M;
3. the flow F of A phase stock liquid transferpump is set
A=100mL/min, the flow F of B phase stock liquid transferpump
B=100mL/min under 25 ℃ of room temperature environments, is delivered to the two-phase stock liquid the continuous mixing reactor in microchannel that channel size is 105 μ m simultaneously, and two phase materials are after evenly differential mixes, and the reaction of serialization integration forms argentiferous calcium phosphate aggregate;
4. reaction product mixture calcium phosphate aggregate colloidal sol is transported to washing/dehydrating device, washes three times, in 60 ℃ of vacuum-dryings to constant weight, obtain non-crystalline state argentiferous calcium phosphate powder.
Collecting the reacted argentiferous calcium phosphate of 100ml aggregate colloidal sol carries out centrifugal, be acid with the upper layer original clear liquid after centrifugal by the nitre acid for adjusting pH, drip again sodium chloride solution and have no silver nitride precipitation, inferring does not have silver ions to run off in clear liquid, illustrate that the silver ions of this technique overwhelming majority has been retained in the calcium phosphate colloid.Dried powder is carried out XRD analysis result such as Fig. 1, be typical non-crystalline state calcium phosphate diffuse peaks, and have no any Ag
+Ionogenic diffraction peak is analyzed as Fig. 2 by SAED in addition, is rendered as dispersion ring, thereby further determines that it is amorphous powder.Carry out composition analysis such as Fig. 3 in conjunction with EDS, confirm to have in powder significant silver content and approach with theoretical input amount, to sum up analytical results judges that this powder is non-crystalline state argentiferous calcium phosphate powder.
Gained non-crystalline state argentiferous calcium phosphate powder is carried out respectively 950 ℃ of insulation 2h obtain the stable argentiferous calcium phosphate microcrystal powder of whiteness, whiteness 90, atomic absorption spectrum test silver content is 2.1wt%.X-ray powder diffraction result such as Fig. 4 are shown as bata-tricalcium phosphate phase and hydroxyapatite heterogeneous calcium phosphate complex mutually, and have no any Ag
+The ion source diffraction peak, hydroxyapatite different from the past carries the silver-colored diffraction peak that occurs obvious simple substance silver 2Theta=38.1 ° of position of understanding after 950 ℃ of pyroprocessing herein.Therefore judge that silver element in the present invention is that the brilliant atom of structure of final product is present in the lattice of product, consists of stable crystallite argentiferous calcium phosphate product.
1.A the preparation of phase stock liquid contains the nitrocalcite of 0.09M, the Silver Nitrate of 0.005M and polyoxyethylene glycol (PEG-1500) solution of 0.3M;
2.B the preparation of phase stock liquid contains the phosphoric acid of 0.06M and the sodium hydroxide solution of 0.18M;
3. the flow F of A phase stock liquid transferpump is set
A=1000mL/min, the flow F of B phase stock liquid transferpump
B=1000mL/min under 50 ℃ of environment, is delivered to the two-phase stock liquid the continuous mixing reactor in microchannel that channel size is 105 μ m simultaneously, and two phase materials are after evenly differential mixes, and the reaction of serialization integration forms argentiferous calcium phosphate aggregate;
4. reaction product mixture calcium phosphate aggregate colloidal sol is transported to washing/dehydrating device, washes three times, in 60 ℃ of vacuum-dryings to constant weight, obtain non-crystalline state argentiferous calcium phosphate powder.Gained non-crystalline state argentiferous calcium phosphate powder is carried out 950 ℃ of insulation 2h obtain the stable argentiferous calcium phosphate microcrystal powder of whiteness, whiteness 90, silver content 5.1wt%.
1.A the preparation of phase stock liquid contains the nitrocalcite of 0.225M, the Silver Nitrate of 0.0056M and polyoxyethylene glycol (PEG-20000) solution of 2.25M;
2.B the preparation of phase stock liquid contains the phosphoric acid of 0.15M and the sodium hydroxide solution of 0.45M;
3. the flow F of A phase stock liquid transferpump is set
A=10mL/min, the flow F of B phase stock liquid transferpump
B=10mL/min under 30 ℃ of room temperature environments, is delivered to the two-phase stock liquid the continuous mixing reactor in microchannel that channel size is 10 μ m simultaneously, and two phase materials are after evenly differential mixes, and the reaction of serialization integration forms argentiferous calcium phosphate aggregate;
4. reaction product mixture calcium phosphate aggregate colloidal sol is transported to washing/dehydrating device, washes three times, in 60 ℃ of vacuum-dryings to constant weight, obtain non-crystalline state argentiferous calcium phosphate powder.Gained non-crystalline state argentiferous calcium phosphate powder is carried out 1300 ℃ of insulation 0.5h obtain the stable argentiferous calcium phosphate microcrystal powder of whiteness, whiteness 95, silver content 2.2wt%.
1.A the preparation of phase stock liquid contains the nitrocalcite of 0.225M, the Silver Nitrate of 0.0056M and polyoxyethylene glycol (PEG-20000) solution of 0.225M;
2.B the preparation of phase stock liquid contains the phosphoric acid of 0.15M and the sodium hydroxide solution of 0.45M;
3. the flow F of A phase stock liquid transferpump is set
A=1000mL/min, the flow F of B phase stock liquid transferpump
B=1000mL/min under 30 ℃ of room temperature environments, is delivered to the two-phase stock liquid the continuous mixing reactor in microchannel that channel size is 200 μ m simultaneously, and two phase materials are after evenly differential mixes, and the reaction of serialization integration forms argentiferous calcium phosphate aggregate;
4. reaction product mixture calcium phosphate aggregate colloidal sol is transported to washing/dehydrating device, washes three times, in 60 ℃ of vacuum-dryings to constant weight, obtain non-crystalline state argentiferous calcium phosphate powder.Gained non-crystalline state argentiferous calcium phosphate powder is carried out 500 ℃ of insulation 10h obtain the stable argentiferous calcium phosphate microcrystal powder of whiteness, whiteness 90, silver content 2.3wt%.
1.A the preparation of phase stock liquid contains the nitrocalcite of 0.1594M, the Silver Nitrate of 0.004M and the phosphoric acid solution of 0.1063M;
2.B the preparation of phase stock liquid contains the potassium hydroxide of 0.5M and the polyoxyethylene glycol of 0.7472M (PEG-1500) solution;
3. the flow F of A phase stock liquid transferpump is set
A=500mL/min, the flow F of B phase stock liquid transferpump
B=320mL/min under 30 ℃ of room temperature environments, is delivered to the two-phase stock liquid the continuous mixing reactor in microchannel that channel size is 105 μ m simultaneously, and two phase materials are after evenly differential mixes, and the reaction of serialization integration forms argentiferous calcium phosphate aggregate;
4. reaction product mixture calcium phosphate aggregate colloidal sol is transported to washing/dehydrating device, the washing secondary, ethanol is washed once, in 60 ℃ of vacuum-dryings to constant weight, obtains non-crystalline state argentiferous calcium phosphate powder.Gained non-crystalline state argentiferous calcium phosphate powder is carried out 950 ℃ of insulation 3h obtain the stable argentiferous calcium phosphate microcrystal powder of whiteness, whiteness 92, silver content 2.1wt%.
1.A the preparation of phase stock liquid contains the nitrocalcite of 0.225M, the Silver Nitrate of 0.0056M and polyoxyethylene glycol (PEG-20000) solution of 0.225M;
2.B the preparation of phase stock liquid contains the Sodium phosphate dibasic of 0.15M and the sodium hydroxide solution of 0.15M;
3. the flow F of A phase stock liquid transferpump is set
A=2500mL/min, the flow F of B phase stock liquid transferpump
B=2500mL/min under 30 ℃ of room temperature environments, is delivered to the two-phase stock liquid the continuous mixing reactor in microchannel that channel size is 200 μ m simultaneously, and two phase materials are after evenly differential mixes, and the reaction of serialization integration forms argentiferous calcium phosphate aggregate;
4. reaction product mixture calcium phosphate aggregate colloidal sol is transported to washing/dehydrating device, the washing secondary, ethanol is washed once, in 60 ℃ of vacuum-dryings to constant weight, obtains non-crystalline state argentiferous calcium phosphate powder.Gained non-crystalline state argentiferous calcium phosphate powder is carried out 1300 ℃ of insulation 2h obtain the stable argentiferous calcium phosphate microcrystal powder of whiteness, whiteness 95, silver content 2.3wt%.
Embodiment 7
1.A the preparation of phase stock liquid contains the nitrocalcite of 0.6376M, the phosphoric acid of 0.4252M, the Silver Nitrate of 0.0124M and polyoxyethylene glycol (PEG-20000) solution of 0.6376M;
2.B the phase stock liquid prepares, and contains the sodium hydroxide solution of 1.2878M;
3. the flow F of A phase stock liquid transferpump is set
A=75mL/min, the flow F of B phase stock liquid transferpump
B=75mL/min under 30 ℃ of room temperature environments, is delivered to the two-phase stock liquid the continuous mixing reactor in microchannel that channel size is 105 μ m simultaneously, and two phase materials are after evenly differential mixes, and the reaction of serialization integration forms argentiferous calcium phosphate aggregate;
4. reaction product mixture calcium phosphate aggregate colloidal sol is transported to washing/dehydrating device, the washing secondary, ethanol is washed once, in 60 ℃ of vacuum-dryings to constant weight, obtains non-crystalline state argentiferous calcium phosphate powder.Gained non-crystalline state argentiferous calcium phosphate powder is carried out 950 ℃ of insulation 2h obtain the stable argentiferous calcium phosphate microcrystal powder of whiteness, whiteness 92, silver content 1.8wt%.
Claims (10)
1. the preparation method of an argentiferous calcium phosphate is characterized in that concrete steps are as follows:
1) stock liquid preparation: with Ca
2+Ion source, PO
4 3-Ion source, Ag
+Ion source, 5 kinds of preparation of raw material of basic cpd and polyoxyethylene glycol become A phase clear liquid and B clear liquid mutually, take water as solvent adjustment A phase clear liquid with the B concentration of clear liquid mutually, with A phase clear liquid and B mutually clear liquid be contained in respectively in two head tanks; Described A phase clear liquid is that at least a kind of preparation of raw material in above-mentioned 5 kinds of raw materials forms, and described B phase clear liquid is that at least a kind of preparation of raw material in above-mentioned 5 kinds of raw materials forms; Described A phase clear liquid and the B final raw material of clear liquid preparation mutually always plant number and must all contain above-mentioned 5 kinds of raw materials;
2) volume pump by source material delivery system by the road with the A phase clear liquid in step 1) and B mutually clear liquid be delivered to the microchannel continuous mixing system, the reaction of serialization integration forms argentiferous calcium phosphate aggregate; The molar ratio of material of whole system: (F
A* C
A-Ca+ F
B* C
B-Ca+ F
A* C
A-Ag+ F
B* C
B-Ag)/(F
A* C
A-P+ F
B* C
B-P)=1.0～2.0, two-phase total flux: F
A+ F
B=10～5000mL/min, in formula, F
ABe the A phase flow rate, unit is mL/min; F
BBe the B phase flow rate, unit is mL/min; C
A-CaFor A mutually in Ca
2+Ionogenic concentration, unit is M; C
B-CaFor B mutually in Ca
2+Ionogenic concentration, unit is M; C
A-AgFor A mutually in Ag
+Ionogenic concentration, unit is M; C
B-AgFor B mutually in Ag
+Ionogenic concentration, unit is M; C
A-PFor A mutually in PO
4 3-Ionogenic concentration, unit is M; C
B-PFor B mutually in PO
4 3-Ionogenic concentration, unit is M;
3) reaction product mixture argentiferous calcium phosphate aggregate colloidal sol is transported to the dehydration washing device, the product after washing is carried out drying, obtain non-crystalline state argentiferous calcium phosphate powder;
4) with step 3) gained non-crystalline state argentiferous calcium phosphate powder through pyroprocessing, obtain the stable argentiferous calcium phosphate microcrystal powder of whiteness.
2. a kind of preparation method of argentiferous calcium phosphate as claimed in claim 1, is characterized in that in step 1) described Ca
2+Ionogenic concentration C
CaBe 0.01～5M; PO
4 3-Ionogenic concentration C
PBe 0.01～5M; Described Ag
+Ion source is selected from Silver Nitrate, and the mol ratio of the add-on of silver ions and the add-on of calcium ion can be 0.001～0.2; The mol ratio of the add-on of described polyoxyethylene glycol and the add-on of calcium ion can be 0.1～10.
3. a kind of preparation method of argentiferous calcium phosphate as claimed in claim 1, is characterized in that in step 1), calculates mole number with the structural unit of polyoxyethylene glycol, and the molecular weight of polyoxyethylene glycol is 1500～20000.
4. a kind of preparation method of argentiferous calcium phosphate as claimed in claim 1, is characterized in that in step 1), and described basic cpd includes but not limited to sodium hydroxide or potassium hydroxide.
5. a kind of preparation method of argentiferous calcium phosphate as claimed in claim 1, is characterized in that in step 1), and the concentration of basic cpd is 0.01～15M.
6. a kind of preparation method of argentiferous calcium phosphate as claimed in claim 1, is characterized in that in step 1), and the temperature of described preparation of raw material process is 15～50 ℃.
7. a kind of preparation method of argentiferous calcium phosphate as claimed in claim 1, it is characterized in that in step 2) in, described volume pump by source material delivery system with the A phase clear liquid in step 1) and B mutually clear liquid be delivered to the microchannel continuous mixing system be under 15～50 ℃ of envrionment conditionss the volume pump by source material delivery system with the A phase clear liquid in step 1) and B mutually clear liquid steadily be delivered to the microchannel continuous mixing system simultaneously.
8. a kind of preparation method of argentiferous calcium phosphate as claimed in claim 1, is characterized in that in step 2) in, described microchannel is of a size of 10～200 μ m; The flow reproducibility error of described volume pump can≤1%, pressure range can be 14.5～1450psi, pressure pulse can≤29psi; The material of pipeline can adopt 316 stainless steels, 316L stainless steel or meet the stainless steel tube of ASTM A269 or equivalent standard, and internal diameter can be 1/16～1 inch, operating pressure can 〉=6000psi.
9. a kind of preparation method of argentiferous calcium phosphate as claimed in claim 1, is characterized in that in step 3), described dry adopt conventional oven dry, lyophilize, spraying drying, supercritical drying or vacuum-drying.
10. a kind of preparation method of argentiferous calcium phosphate as claimed in claim 1, is characterized in that in step 4), and the temperature of described pyroprocessing is 500～1300 ℃, and the atmosphere of processing is air, and the time of processing is 0.5～10h.
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| CN108785106B (en) * | 2018-06-05 | 2021-03-16 | 中国科学院上海硅酸盐研究所 | Colloidal silver-containing calcium phosphate nanocomposite and preparation method and application thereof |
| CN108946690A (en) * | 2018-07-02 | 2018-12-07 | 昆明理工大学 | A kind of preparation method of antibacterial modified hydroxyapatite material |
| WO2021157662A1 (en) * | 2020-02-04 | 2021-08-12 | 国立研究開発法人産業技術総合研究所 | Crystal, powder, block material, porous object, bone filler material, and oral bone filler material of calcium phosphate, method for producing calcium phosphate crystal, method for producing block material, and method for producing porous object |
| JPWO2021157662A1 (en) * | 2020-02-04 | 2021-08-12 | ||
| JP7410586B2 (en) | 2020-02-04 | 2024-01-10 | 国立研究開発法人産業技術総合研究所 | Calcium phosphate crystals, powders, block materials, porous bodies, bone grafting materials and oral bone grafting materials, and methods for producing calcium phosphate crystals, block materials, and porous bodies |
| JP7474454B1 (en) | 2022-11-01 | 2024-04-25 | 国立大学法人 名古屋工業大学 | Method for modifying crystalline calcium phosphate particles to amorphous calcium phosphate by wet grinding |
| WO2024095956A1 (en) * | 2022-11-01 | 2024-05-10 | 国立大学法人 名古屋工業大学 | Method for modifying crystalline calcium phosphate particles into amorphous calcium phosphate by wet grinding |
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