CN103110978A - Tissue filling material, its preparation method and compound containing it - Google Patents
Tissue filling material, its preparation method and compound containing it Download PDFInfo
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- CN103110978A CN103110978A CN2011103627872A CN201110362787A CN103110978A CN 103110978 A CN103110978 A CN 103110978A CN 2011103627872 A CN2011103627872 A CN 2011103627872A CN 201110362787 A CN201110362787 A CN 201110362787A CN 103110978 A CN103110978 A CN 103110978A
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Abstract
The invention relates to a tissue filling material, its preparation method and a compound containing it. The method includes the following steps: providing a solution containing calcium ions and a phosphate solution; mixing the solution containing calcium ions with the phosphate solution to obtain a mixed solution; heating and stirring the mixed solution; filtering the mixed solution to obtain a precipitate; drying the precipitate; calcining the dried precipitate; and grinding the calcined precipitate to obtain the tissue filling material. The method is simple and practical, and the prepared tissue filling material is a pore-free ceramic material, has small particle sizes and is helpful for the interaction with biological tissues.
Description
Technical field
The present invention is about a kind of tissue filling material, espespecially a kind of tissue filling material that is comprised of ceramic material.
Background technology
When skeleton because of external force or aging when damaging to some extent, except operating treatment, usually also need the implantable bone packing material assisting to keep the normal start of skeleton, and promote tissue to restore.These packing materials can be divided into metal material, macromolecular material, ceramic material, composite and natural material etc.Metal material and macromolecular material are the packing materials that is widely used in the earliest clinically, and in 20 th century later, and the doctor's pottery of giving birth to of bio-compatibility excellence is developed gradually, and stablize chemical bonded refractory and more and more come into one's own because it can form with tissue.
Animal skeleton mainly is made of body calcium (body calcium) and body phosphorus (body phosphate).Accordingly, commonly use in the field in as the composition of the ceramic material of tissue filling material take synthos as main, and have the structure of multiple hole; Wherein, the constituent of oxyhydrogen-base apatite is all similar to the inanimate matter of skeleton with structure, and is easy to form chemical bonded refractory with biological tissue, is modal ceramic material composition therefore.Other common composition for forming this ceramic material still has tricalcium phosphate, calcium pyrophosphate, tetracalcium phosphate, fluor-apatite etc.Research points out that these ceramic materials are the high bio-compatibility of tool not only, more helps the regeneration of both injured bones tissue.
Except the filling and repairing of osseous tissue, aforementioned ceramic material is the sharp implant that is used to as the plastic surgery operation also, and it can stimulate the collagen protein in the body newborn, is used to be called crystallite porcelain (Radiance) in the field.By these information as can be known, the utilization of the packing material that is comprised of synthos is extensive, has very high value.Yet, in the still difficult meaning perfection of method for making of aforementioned ceramic material, for the utilization in response to the increasing market demand and different field, develop a kind of simple and practical ceramic mould tissue filling material preparation method between industry, truly have its necessity.
Summary of the invention
A purpose of the present invention is for providing a kind of tissue filling material preparation method, and its step is simple, is conducive to the utilization between industry.
Another purpose of the present invention is for providing a kind of tissue filling material and containing its complex, and it is conducive to fill up fault location tiny in the tissue, and and biological tissue between better reciprocal action is arranged, and therefore help transmitting tissue newborn.
For achieving the above object, the invention provides a kind of tissue filling material preparation method, it comprises following steps: a calcium ions solution and monophosphate solution are provided; Aforementioned calcium ions solution and aforementioned phosphate solution are mixed into a mixed liquor; Heating is also stirred aforementioned mixed liquor; Filter aforementioned mixed liquor to obtain a precipitate; Dry aforementioned precipitate; Make state precipitate before dry and carry out calcination after; And ground before calcination and state precipitate, to obtain aforementioned tissue filling material.
Preferably, in the aforementioned mixed liquor, the molar concentration ratio of phosphate anion and calcium ion is 0.5 ~ 1.2.
Preferably, aforementioned calcium ions solution is calcium nitrate solution, calcium hydroxide, calcium carbonate, calcium sulfate, calcium silicates or its combination.
Preferably, its aforementioned phosphate solution is DAP solution, potassium dihydrogen phosphate, ammonium di-hydrogen phosphate, sodium phosphate or its combination.
Preferably, aforementioned calcination is the two-part calcination.Preferably, the temperature of the phase I of aforementioned two-part calcination is 550 ~ 790 ℃, and the temperature of second stage is 1210 ~ 1500 ℃.
Preferably, the pH value of aforementioned calcium ions solution is 9 ~ 12.
Preferably, the pH value of aforementioned phosphate solution is 9 ~ 12.
The method of preferably, aforementioned calcium ions solution and aforementioned phosphate solution being mixed is for to enter aforementioned phosphate solution with the titration of aforementioned calcium ions solution.
Preferably, the flow velocity of aforementioned titration is 15 ~ 18 ml/min.
Preferably, aforementioned heating and the temperature that stirs aforementioned mixed liquor are 80 ~ 100 ℃.
Preferably, before filtering aforementioned mixed liquor, aforementioned mixed liquor is left standstill.Preferably, the aforementioned time of leaving standstill is 20 ~ 36 hours.
Preferably, the method for the aforementioned mixed liquor of aforementioned filtration is centrifuging.
Preferably, the aforementioned sedimentary method of aforementioned drying is spray drying, vacuum drying, lyophilization, drying with superheated steam or its combination.
Preferably, it further comprises a step, sieves with the powder of aforementioned grinding being stated the precipitate gained before calcination.
The present invention provides again a kind of tissue filling material, and it comprises: the oxyhydrogen-base apatite of 60 ~ 70wt%: and the tricalcium phosphate of 40 ~ 30wt%.
The present invention provides a kind of tissue filling complex again, and it comprises: the aforementioned tissue filling material of 40 ~ 60 wt%; And the medical acceptable excipient of 60 ~ 40 wt%.
Preferably, the particle diameter of aforementioned tissue filling material is not more than 15 microns.Preferably, the particle diameter of aforementioned tissue filling material is 5 ~ 15 microns.
Preferably, aforementioned tissue filling material is without hole tissue filling material.
Preferably, aforementioned tissue filling material is obtained by preceding method.
Preferably, aforementioned excipients comprises starch, lactose, sucrose, microcrystalline Cellulose, glycerol, sodium carboxymethyl cellulose, water or its combination.Preferably, aforementioned excipients comprises: the glycerol of 11 ~ 17 wt%; 0.9 the sodium carboxymethyl cellulose of ~ 1.3wt%; And the water of 81.7 ~ 88.1 wt%.
In sum, method of the present invention is adopted chemical method, and cooperates the two-part calcination, has simple and practical advantage.In addition, tissue filling material of the present invention has suitable component ratio, and is conducive to and the interactive particle diameter of organizing, and therefore helps to stimulate tissue newborn.
Description of drawings
Fig. 1 is the ultramicroscope image of the tissue filling material of the embodiment of the invention one, (A) 1000 times, and (B) 4000 times.
Fig. 2 is the X-ray diffraction analysis figure of the tissue filling material of the embodiment of the invention one.
The specific embodiment
The present invention and about a kind of tissue filling material and contain its tissue filling complex.Aforementioned tissue filling material composite comprises oxyhydrogen-base apatite and the tricalcium phosphate of proper proportion.Oxyhydrogen-base apatite is known to be applicable to as packing material, and the material that tricalcium phosphate is another kind to come into one's own.Because tricalcium phosphate is more unstable in biological tissue, therefore in case with after biological tissue contact, just can decompose lentamente and calcium ion and phosphonium ion are released in the tissue, help the new life of transmitting tissue.
Accordingly, tissue filling material preparation method of the present invention, the ceramic material that has oxyhydrogen-base apatite and tricalcium phosphate advantage concurrently is prepared in combinatorial chemical method and two-part calcination, and its step comprises.
One calcium ions solution and monophosphate solution at first are provided.Aforementioned calcium ions solution and aforementioned phosphate solution are in order to carry out chemical reaction to generate synthos.Aforementioned calcium ions solution comprises, but is not limited to calcium nitrate solution, calcium hydroxide, calcium carbonate, calcium sulfate, calcium silicates or its combination.Aforementioned phosphate solution comprises, but is not limited to DAP solution, potassium dihydrogen phosphate, ammonium di-hydrogen phosphate, sodium phosphate or its combination.
Preferably, the pH value with aforementioned calcium ions solution and/or aforementioned phosphate solution is adjusted into 9～12.Under the field have and know that usually the knowledgeable when selecting to adjust the mode of pH value not affecting in the situation that subsequent chemical reaction carries out, for example, adds ammonia, until desired pH value in aforementioned calcium ions solution and/or aforementioned phosphate solution.
Then, aforementioned calcium ions solution and aforementioned phosphate solution are mixed into a mixed liquor.More clearly, utilize burette that aforementioned calcium ions solution is added aforementioned phosphate solution.Preferably, the speed of titration is 15～18 milliliters of per minutes.Simultaneously, the process in titration needs fully to stir so that aforementioned calcium ions solution and aforementioned phosphate solution mix fully.More clearly, aforementioned mixed liquor is rocked, to reach the purpose of certain reaction under rotating speed 900 ~ 1200 RPM.Preferably, after mixing, in aforementioned mixed liquor, the molar concentration ratio of phosphate anion and ionic calcium soln is 0.5 ~ 1.2.
When aforementioned calcium ions solution and aforementioned phosphate solution in aforementioned mixed liquor, fully mix and reaction after, can generate white pasty state precipitate.Then, continue under 80～100 ℃, to stir aforementioned mixed liquors 1～2 hour.Then, aforementioned mixed liquor was left standstill 20～36 hours; Preferably, leave standstill more than 1 day.Filter aforementioned mixture to obtain aforementioned precipitate thereafter.Preferably, can adopt centrifuging, under the condition of rotating speed 200 ~ 500 RPM, with aforementioned precipitate and unreacted ion isolation.Known filter method in field if can reach the same effect, also can be selected in the method for the present invention under other.Then, make aforementioned drying precipitate.Dry aforementioned sedimentary method includes, but are not limited to: spray drying, vacuum drying, lyophilization, drying with superheated steam or its combination.
Then, make drying state precipitate before and carry out calcination.More clearly, aforementioned calcination is the two-part calcination, and the temperature of its phase I is 550 ~ 790 ℃, and the temperature of second stage is 1210 ~ 1500 ℃.Preferably, the programming rate of aforementioned calcination is 5 ~ 15 ℃ of per minutes.Preferably, the time of aforementioned phase I and/or aforementioned second stage is 2 ~ 4 hours.After the two-part calcination is finished, make the aforementioned precipitate through calcination naturally cool to room temperature.
At last, grind aforementioned precipitate, and it is sieved, to obtain the tissue filling material of the desired particle diameter of tool the present invention.The mode of aforementioned grinding need not limit, and the grinding facility of commonly using in the field under can adopting are carried out.Aforementioned mode of sieving need not limit, and the sieve shaker of commonly using in the field under can adopting is carried out.Preferably, the hole of the employed screen cloth of aforementioned sieve shaker is 25 ~ 40 microns.The particle diameter of tissue filling material of the present invention is for being not more than 15 microns; Preferably, be 5～15 microns.
Accordingly, tissue filling material of the present invention has less particle diameter, therefore is particularly suitable for filling up small defective in tissue.More very it, the tissue filling material that particle diameter is less will help the reciprocal action with biological tissue, further stimulate tissue newborn.
For use clinically, making the aforementioned tissue filling material and the medical acceptable mixed with excipients that make is a tissue filling complex; More clearly, aforementioned tissue filling material accounts for 40 ~ 60 wt% of whole complex, and aforementioned excipients accounts for 60 ~ 40 wt% of whole complex.Aforementioned excipients includes, but are not limited to starch, lactose, sucrose, microcrystalline Cellulose, glycerol, sodium carboxymethyl cellulose, water or its combination.Preferably, aforementioned excipients comprises glycerol, sodium carboxymethyl cellulose and water; More clearly, comprise the glycerol of 11 ~ 17 wt%, the sodium carboxymethyl cellulose of 0.9 ~ 1.3 wt% and the water of 81.7 ~ 88.1 wt%.
Following examples are only with literal and the actual processing procedure that carries out of the graphic explanation of arranging in pairs or groups and experiment, so that the person with usual knowledge in their respective areas more clearly understands characteristics of the present invention and spirit.Only should be noted that following examples only are used for the present invention exemplarily is described, and do not use to limit interest field of the present invention.
Embodiment one: prepare tissue filling material of the present invention and contain its complex.
In present embodiment, use calcium nitrate solution and DAP solution as raw material, and, with ammonia the pH value of aforementioned calcium nitrate solution and aforementioned DAP solution is adjusted into 11.Adopt the mode of titration, with the flow velocity of 17 ml/min, aforementioned calcium nitrate solution is added formation one mixed liquor in the aforementioned DAP solution, and continue intensely stirring (1000 RPM).After the mixing, in aforementioned mixed liquor, the molar concentration rate of phosphate anion and calcium ion is 0.8:1.The temperature that then will separate out gradually sedimentary aforementioned mixed liquor is increased to 100 ℃.Keep this temperature and continue stirring until few 1 hour.Afterwards, left standstill aforementioned mixed liquor at least 1 day.
Then, with the centrifugal aforementioned mixed liquor of rotating speed 200 RPM, so that precipitate wherein and unreacted ion isolation.Then, again in the spray drying mode, make aforementioned precipitate lower dry in 25 ℃.Thereafter, make drying state precipitate before again and carry out the two-part calcination, the temperature of its phase I is 750 ℃, and the temperature of second stage is 1250 ℃.The calcination of aforementioned phase I and the calcination of aforementioned second stage all continue 2 hours.
Then, grind behind the aforementioned precipitate of calcination with grinder, sieve take sieve shaker (the screen cloth hole is as 40 microns), obtain the tissue filling material of present embodiment.At last, aforementioned tissue filling material is fully mixed with excipient (water of the glycerol of 15wt%, the sodium carboxymethyl cellulose of 1.1wt% and 83.9wt%), can obtain the tissue filling complex of present embodiment.
Embodiment two: the tissue filling material character of embodiment one is analyzed.
In present embodiment, detect among the embodiment one according to the prepared tissue filling material character of method of the present invention.
At first please refer to the drawing 1, and it shows the SEM image of the tissue filling material of embodiment one, and wherein (A) figure is the image of 1000 times of amplifications, and (B) figure is the image of 4000 times of amplifications.By the SEM image as can be known, tissue filling material of the present invention is without the hole ceramic material.In addition, can judge that by scale the particle diameter of tissue filling material of the present invention is at 5～15 microns, belongs to the ceramic material of micron grade simply.
Please refer to the drawing 2 again, and it shows the X-ray diffraction analysis figure (XRD) of the tissue filling material of embodiment one.The result who is analyzed by X-ray diffraction analysis instrument (X-ray Diffractometer) as can be known, the composition of the tissue filling material of embodiment one is mainly take oxyhydrogen-base apatite as main, and contains the tricalcium phosphate of trace.Further contain the oxyhydrogen-base apatite of 70 wt% and the tricalcium phosphate of 30 wt% with the tissue filling material of learning embodiment one behind the X-ray diffraction analysis.
Claims (20)
1. tissue filling material preparation method is characterized in that it comprises following steps:
One calcium ions solution and monophosphate solution are provided;
Aforementioned calcium ions solution and aforementioned phosphate solution are mixed into a mixed liquor;
Heating is also stirred aforementioned mixed liquor;
Filter aforementioned mixed liquor to obtain a precipitate;
Dry aforementioned precipitate;
After making dry aforementioned precipitate carry out calcination; And
Grinding is through the aforementioned precipitate of calcination, to obtain aforementioned tissue filling material.
2. the method for claim 1, wherein in the aforementioned mixed liquor, the molar concentration ratio of phosphate anion and calcium ion is 0.5 ~ 1.2.
3. the method for claim 1, wherein aforementioned calcium ions solution is calcium nitrate solution, calcium hydroxide, calcium carbonate, calcium sulfate, calcium silicates or its combination.
4. the method for claim 1, wherein aforementioned phosphate solution is DAP solution, potassium dihydrogen phosphate, ammonium di-hydrogen phosphate, sodium phosphate or its combination.
5. the method for claim 1, wherein aforementioned calcination is the two-part calcination.
6. method as claimed in claim 5, wherein the temperature of the phase I of aforementioned two-part calcination is 550 ~ 790 ℃, the temperature of second stage is 1210 ~ 1500 ℃.
7. the method for claim 1, wherein the pH value of aforementioned calcium ions solution and phosphate solution is 9 ~ 12.
8. the method for claim 1, the method for wherein aforementioned calcium ions solution and aforementioned phosphate solution being mixed is for to enter aforementioned phosphate solution with the titration of aforementioned calcium ions solution.
9. method as claimed in claim 8, wherein the flow velocity of aforementioned titration is 15 ~ 18 ml/min.
10. the method for claim 1, wherein aforementioned heating and the temperature that stirs aforementioned mixed liquor are 80 ~ 100 ℃.
11. the method for claim 1 wherein before filtering aforementioned mixed liquor, makes first aforementioned mixed liquor leave standstill 20 ~ 36 hours.
12. the method for claim 1, wherein the aforementioned sedimentary method of aforementioned drying is spray drying, vacuum drying, lyophilization, drying with superheated steam or its combination.
13. the method for claim 1, it further comprises a step, sieves with the powder of aforementioned grinding being stated the precipitate gained before calcination.
14. a tissue filling material, it comprises:
The oxyhydrogen-base apatite of 60 ~ 70wt%; And
The tricalcium phosphate of 30 ~ 40wt%.
15. tissue filling material as claimed in claim 14, its particle diameter are 5 ~ 15 microns.
16. tissue filling material as claimed in claim 14, it is without hole tissue filling material.
17. tissue filling material as claimed in claim 14, it is obtained by method claimed in claim 1.
18. a tissue filling complex, it comprises:
The tissue filling material as claimed in claim 14 of 40 ~ 60 wt%; And
The medical acceptable excipient of 60 ~ 40 wt%.
19. complex as claimed in claim 18, wherein aforementioned excipients comprises starch, lactose, sucrose, microcrystalline Cellulose, glycerol, sodium carboxymethyl cellulose, water or its combination.
20. complex as claimed in claim 19, wherein aforementioned excipients comprises:
The glycerol of 11 ~ 17 wt%;
0.9 the sodium carboxymethyl cellulose of ~ 1.3wt%; And
81.7 the water of ~ 88.1 wt%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103342555A (en) * | 2013-07-05 | 2013-10-09 | 北京北达燕园微构分析测试中心有限公司 | Strontium magnesium-doped nano-hydroxyapatite and preparation method thereof |
| TWI494270B (en) * | 2013-07-15 | 2015-08-01 | Botanical added to biowaste synthetic calcium hydroxyapatite method |
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Application publication date: 20130522 |