CN103816572A - Preparation method of injectable porous calcium phosphate bone repair material - Google Patents
Preparation method of injectable porous calcium phosphate bone repair material Download PDFInfo
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- CN103816572A CN103816572A CN201410071625.7A CN201410071625A CN103816572A CN 103816572 A CN103816572 A CN 103816572A CN 201410071625 A CN201410071625 A CN 201410071625A CN 103816572 A CN103816572 A CN 103816572A
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Abstract
The invention discloses a preparation method of an injectable porous calcium phosphate bone repair material. the method provided by the invention is as follows: dicalicium phosphate anhydrous is firstly prepared while chitosan, citric acid and a glucose solution are prepared; mannitol crystals are prepared for later use; chitosan, citric acid and the glucose solution are adopted as a liquid phase, and tetracalcium phosphate and dicalicium phosphate anhydrous are adopted as a solid phase; a pore-forming agent which is composed of mannitol and a polylactic acid-glycolic acid copolymer is added into the solid phase; the solid phase and the liquid phase are successively added into a small culture dish and rapidly stirred with a glass rod for 1-2min so as to form uniform pulp; and the mixture initially has injectable performance, and the porous bone repair material is formed after solidification of the mixture. The repair material prepared by the method has advantages of short solidification time and high compressive strength. Through SEM observation of surface morphology, communication between pores is good. By the preparation method, plasticity and viscoelasticity of CPC can be raised, bone cement is endowed with injectable performance, and application range and application comfort level of bone cement are raised greatly.
Description
Technical field
The present invention relates to medical material technical field, relate in particular to a kind of preparation method of injectable porous calcium phosphate bone renovating material.
Background technology
Along with deepening continuously to field of medical materials research, osseous tissue renovating material particularly calcium phosphorus based material receives people's concern day by day, it has good biocompatibility, good bone conductibility and osteoinductive potential, has huge potentiality in the clinical practice of bone reparation.But there is mechanical property poor,
Setting time is long, porosity is low and the slow shortcoming of degrading, and can not meet the related request of bone tissue engineering stent material.
Calcium phosphate bone cement (CPC) exists the shortcoming that setting time is long, mechanical property is poor and porosity is low, can not meet the requirement of bone tissue engineering stent material.
Summary of the invention
For the above-mentioned deficiency of calcium phosphate bone cement, the present invention prepares the injectable calcium orthophosphate base bone renovating material that can meet the reparation application of clinical Wicresoft, this material is take calcium phosphate bone cement as primary structure, liquid phase adopts the weak acid solution of chitosan, to improve plasticity and the viscoelasticity of CPC, make bone cement there is syringeability, greatly promote range of application and the application comfort level of bone cement; Solid phase is biphasic calcium phosphate (TTCP+DCPA) powder body respectively, and in solid phase, add a certain amount of mannitol, and Poly(D,L-lactide-co-glycolide (PLGA) is as pore creating material, when mannitol dissolves in vivo, CPC forms loose structure gradually, the osmotic dehydration of simultaneously avoiding the mannitol of higher concentration to produce cell, utilize the mannitol dissolubility different from PLGA to make material have in early days some strength, progressively pore-forming in body, thus make one " injectable timbering material ".
The present invention adopts following technical scheme:
The concrete steps of the preparation method of injectable porous calcium phosphate bone renovating material of the present invention are as follows:
(1) dicalcium phosphate dehydrate is processed to 12h at 120 ℃, sieve after cooling, and then put into ball mill, add agate ball and dehydrated alcohol, on ball mill, respectively after ball milling 12h, in the drying baker of 80 ℃, dry and make calcium phosphate dibasic anhydrous;
(2) by chitosan, citric acid, glucose by mass percentage the ratio of 1-5%, 2-8%, 10-20% be dissolved in deionized water, stirring and dissolving, wiring solution-forming, leave standstill 24h, for subsequent use;
(3) by mannitol, the alcoholic solution being placed in, heated and stirred, make it abundant dissolving, the volume ratio of mannitol and ethanol is 1-3: 1, and then second leave standstill the cooling liquor-saturated crystal of manna that obtains recrystallization, by the mannitol crystal vacuum filtration after recrystallization, dry, cross respectively 50 mesh sieves and 150 mesh sieves, for subsequent use;
(4) liquid phase adopts the solution of step (2) configuration, the calcium phosphate dibasic anhydrous that solid phase is prepared by tetracalcium phosphate and step (1) forms, solid-to-liquid ratio is 0.5-1g/ml, first in solid phase, add porogen, the addition of porogen is the 15-25% of solid phase weight, mannitol and Poly(D,L-lactide-co-glycolide that porogen is prepared by step (3) form, then biphase solid-liquid priority is joined in little culture dish, stir rapidly 1-2min with Glass rod, form uniform slurry, this mixture initially all has syringeability, solidify rear formation porous bone repair material.
In step (1), dicalcium phosphate dehydrate is analytical pure.
In step (2), preferably by chitosan, citric acid, glucose by mass percentage 3%, 5%, 15% ratio be dissolved in deionized water.
In step (2), preferably by chitosan, citric acid, glucose by mass percentage 5%, 8%, 20% ratio be dissolved in deionized water.
In step (3), preferably the volume ratio of mannitol and ethanol is 2: 1.
In step (3), preferably the volume ratio of mannitol and ethanol is 1: 1.
In step (4), the weight ratio of calcium phosphate dibasic anhydrous prepared by tetracalcium phosphate and step (1) is 0.5-3: 1.
In step (4), the weight ratio of calcium phosphate dibasic anhydrous prepared by preferably phosphoric acid four calcium and step (1) is 1: 1.
In step (4), the particle diameter of tetracalcium phosphate is 0-20 μ m, purity >=99%.
In step (4), preferably solid-to-liquid ratio is 0.8g/ml.
In step (4), preferably solid-to-liquid ratio is 1g/ml.
In step (4), preferably the addition of porogen is 20% of solid phase weight.
In step (4), preferably the addition of porogen is 25% of solid phase weight.
In step (4), in porogen, the mol ratio of mannitol and Poly(D,L-lactide-co-glycolide is 0.5-3: 1.
In step (4), preferably in porogen, the mol ratio of mannitol and Poly(D,L-lactide-co-glycolide is 2: 1.
In step (4), preferably in porogen, the mol ratio of mannitol and Poly(D,L-lactide-co-glycolide is 3: 1.
The liquid phase of calcium phosphate bone cement being carried out to modification, adopt the weak acid solution of chitosan as liquid phase. chitosan has good biocompatibility, and the slant acidity of solution can make CPC solid phase powder be easy to dissolve, and the process of acceleration of hydration reaction, shortens setting time.
On the basis of biphasic calcium phosphate system CPC, development of new porous C PC timbering material.This material adopts soluble fiber mannitol and PLGA as porogen, utilizes its feature and calcium phosphate bone cement that can dissolve under body fluid environment compound, the calcium phosphate cement bracket material material that preparation can vivo degradation pore-forming.
The preparation method of injectable porous calcium phosphate bone renovating material of the present invention has following technique effect:
Porous calcium phosphate bone renovating material prepared by method of the present invention has setting time short (9.20 ± 0.5min), the advantage of comprcssive strength high (33.8 ± 0.5MPa).Configuration of surface is good by scanning electron microscopic observation Kong Jian UNICOM.The present invention can improve plasticity and the viscoelasticity of CPC, makes bone cement have syringeability, greatly promotes range of application and the application comfort level of bone cement.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph that does not add the porous calcium phosphate bone renovating material of porogen.
Fig. 2 is the scanning electron microscope (SEM) photograph of the porous calcium phosphate bone renovating material prepared of embodiment 1.。
The specific embodiment
The following examples are to describe in further detail of the present invention.
Embodiment 1
(1) dicalcium phosphate dehydrate is processed to 12h at 120 ℃, sieve after cooling, and then put into ball mill, add agate ball and dehydrated alcohol, on ball mill, respectively after ball milling 12h, in the drying baker of 80 ℃, dry and make calcium phosphate dibasic anhydrous;
(2) by chitosan, citric acid, glucose by mass percentage 3%, 5%, 15% ratio be dissolved in deionized water, stirring and dissolving, wiring solution-forming, leave standstill 24h, for subsequent use;
(3) by mannitol, the alcoholic solution being placed in, heated and stirred, make it abundant dissolving, the volume ratio of mannitol and ethanol is 2: 1, and then second leave standstill the cooling liquor-saturated crystal of manna that obtains recrystallization, by the mannitol crystal vacuum filtration after recrystallization, dry, cross respectively 50 mesh sieves and 150 mesh sieves, for subsequent use;
(4) liquid phase adopts the solution of step (2) configuration, the calcium phosphate dibasic anhydrous that solid phase is prepared by tetracalcium phosphate and step (1) forms, solid-to-liquid ratio is 0.8g/ml, first in solid phase, add porogen, the addition of porogen is 20% of solid phase weight, mannitol and Poly(D,L-lactide-co-glycolide that porogen is prepared by step (3) form, then biphase solid-liquid priority is joined in little culture dish, stir rapidly 1-2min with Glass rod, form uniform slurry, this mixture initially all has syringeability, solidify rear formation porous bone repair material.
In step (4), in porogen, the mol ratio of mannitol and Poly(D,L-lactide-co-glycolide is 2: 1.
Embodiment 2
(1) dicalcium phosphate dehydrate is processed to 12h at 120 ℃, sieve after cooling, and then put into ball mill, add agate ball and dehydrated alcohol, on ball mill, respectively after ball milling 12h, in the drying baker of 80 ℃, dry and make calcium phosphate dibasic anhydrous;
(2) by chitosan, citric acid, glucose by mass percentage 5%, 8%, 20% ratio be dissolved in deionized water, stirring and dissolving, wiring solution-forming, leave standstill 24h, for subsequent use;
(3) by mannitol, the alcoholic solution being placed in, heated and stirred, make it abundant dissolving, the volume ratio of mannitol and ethanol is 1: 1, and then second leave standstill the cooling liquor-saturated crystal of manna that obtains recrystallization, by the mannitol crystal vacuum filtration after recrystallization, dry, cross respectively 50 mesh sieves and 150 mesh sieves, for subsequent use;
(4) liquid phase adopts the solution of step (2) configuration, the calcium phosphate dibasic anhydrous that solid phase is prepared by tetracalcium phosphate and step (1) forms, solid-to-liquid ratio is 1g/ml, first in solid phase, add porogen, the addition of porogen is 25% of solid phase weight, mannitol and Poly(D,L-lactide-co-glycolide that porogen is prepared by step (3) form, then biphase solid-liquid priority is joined in little culture dish, stir rapidly 1-2min with Glass rod, form uniform slurry, this mixture initially all has syringeability, solidify rear formation porous bone repair material.
In step (4), in porogen, the mol ratio of mannitol and Poly(D,L-lactide-co-glycolide is 3: 1.
Embodiment 3
(1) dicalcium phosphate dehydrate is processed to 12h at 120 ℃, sieve after cooling, and then put into ball mill, add agate ball and dehydrated alcohol, on ball mill, respectively after ball milling 12h, in the drying baker of 80 ℃, dry and make calcium phosphate dibasic anhydrous;
(2) by chitosan, citric acid, glucose by mass percentage 1%, 8%, 10% ratio be dissolved in deionized water, stirring and dissolving, wiring solution-forming, leave standstill 24h, for subsequent use;
(3) by mannitol, the alcoholic solution being placed in, heated and stirred, make it abundant dissolving, the volume ratio of mannitol and ethanol is 3: 1, and then second leave standstill the cooling liquor-saturated crystal of manna that obtains recrystallization, by the mannitol crystal vacuum filtration after recrystallization, dry, cross respectively 50 mesh sieves and 150 mesh sieves, for subsequent use;
(4) liquid phase adopts the solution of step (2) configuration, and solid phase is the nothing of being prepared by tetracalcium phosphate and step (1)
Water calcium hydrogen phosphate composition, solid-to-liquid ratio is 0.5g/ml, first in solid phase, add porogen, the addition of porogen is 15% of solid phase weight, mannitol and Poly(D,L-lactide-co-glycolide that porogen is prepared by step (3) form, then biphase solid-liquid priority is joined in little culture dish, stir rapidly 1-2min with Glass rod
Form uniform slurry, this mixture initially all has syringeability, solidifies rear formation porous bone repair material.
In step (4), in porogen, the mol ratio of mannitol and Poly(D,L-lactide-co-glycolide is 1: 1.
Embodiment 4
Respectively to the mol ratio of mannitol and Poly(D,L-lactide-co-glycolide (PLGA) at 2: 1 and 1: 1 time, add the porous calcium phosphate bone renovating material that makes of not commensurability porogen and carry out performance measurement, result as shown in Table 1 and Table 2.
Table 1 mannitol/PLGA2: 1 group
Table 2 mannitol/PLGA1: 1 group
In upper table, measured respectively mannitol/PLGA2: 1 group from mannitol/PLGA1: the variation of 1 group of material key data under different porogen ratios.Fig. 1 shows under the scanning electron microscope of material while not adding porogen, Fig. 2 is that mannitol/PLGA (2: 1) group porogen accounts for 20% cross-section morphology, visible section loose degree increases, it is many that cavity becomes, pore size differs, large aperture is relatively many, the mutual UNICOM in visible several large apertures in Fig. 2, and this structure is conducive to the growth of cell.Can be seen and in the aperture differing in size, be mingled with not yet consoluet bar shaped filamentary structure by Fig. 2, this fibre structure can strengthen the anti-tractive intensity of sample effectively simultaneously, and it can increase the UNICOM between aperture after dissolving effectively.In this figure, visible crystals is grown very intactly, has the crystal such as needle-like, lamellar, column, and some gelatinous mass microgranules are filled in the space of crystalline framework, and the various crystal overlap joint that intermeshes, forms strong skeleton, form a three-dimensional space strong bonded,
Closely knit entirety.
Can find that by table 1 and table 2 porogen adopts the bone cement porosity 50 ± 0.5% of mannitol/PLGA (2: the 1) gained that adds 20%, comprcssive strength 35 ± 0.8MPa, setting time 13.5 ± 0.2min.Comparatively compound clinical needs.In a word: adopt biphasic calcium phosphate (tetracalcium phosphate TTCP: calcium hydrogen phosphate DCPA is 1: 1) powder body, add 20% mannitol/PLGA (2:1) as porogen, after mix homogeneously, liquid phase adopts 3% chitosan (wt%)+5% citric acid (wt%)+15% glucose (wt%) mixed solution, according to solid-to-liquid ratio 0.8 mix homogeneously, prepare calcium phosphate bone cement material porosity 50 ± 0.5%, comprcssive strength 35 ± 0.8MPa, setting time 13.5 ± 0.2min, configuration of surface is good by scanning electron microscopic observation Kong Jian UNICOM.It is a kind of injectable porous bone repair material.
Although illustrated and described embodiments of the invention, for the ordinary skill in the art, be appreciated that without departing from the principles and spirit of the present invention and can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claims and equivalent thereof.
Claims (10)
1. a preparation method for injectable porous calcium phosphate bone renovating material, is characterized in that: the concrete steps of described method are as follows:
(1) dicalcium phosphate dehydrate is processed to 12h at 120 ℃, sieve after cooling, and then put into ball mill, add agate ball and dehydrated alcohol, on ball mill, respectively after ball milling 12h, in the drying baker of 80 ℃, dry and make calcium phosphate dibasic anhydrous;
(2) by chitosan, citric acid, glucose by mass percentage the ratio of 1-5%, 2-8%, 10-20% be dissolved in deionized water, stirring and dissolving, wiring solution-forming, leave standstill 24h, for subsequent use;
(3) by mannitol, be placed in alcoholic solution, heated and stirred, make it abundant dissolving, the volume ratio of mannitol and ethanol is 1-3: 1, and then second leave standstill the cooling liquor-saturated crystal of manna that obtains recrystallization, by the mannitol crystal vacuum filtration after recrystallization, dry, cross respectively 50 mesh sieves and 150 mesh sieves, for subsequent use;
(4) liquid phase adopts the solution of step (2) configuration, the calcium phosphate dibasic anhydrous that solid phase is prepared by tetracalcium phosphate and step (1) forms, solid-to-liquid ratio is 0.5-1g/ml, first in solid phase, add porogen, the addition of porogen is the 15-25% of solid phase weight, mannitol and Poly(D,L-lactide-co-glycolide that porogen is prepared by step (3) form, then biphase solid-liquid priority is joined in little culture dish, stir rapidly 1-2min with Glass rod, form uniform slurry, this mixture initially all has syringeability, solidify rear formation porous bone repair material.
2. preparation method as claimed in claim 1, is characterized in that: in step (1), dicalcium phosphate dehydrate is analytical pure.
3. preparation method as claimed in claim 1, is characterized in that: in step (2), by chitosan, citric acid, glucose by mass percentage 3%, 5%, 15% ratio be dissolved in deionized water.
4. preparation method as claimed in claim 1, is characterized in that: in step (3), the volume ratio of mannitol and ethanol is 2: 1.
5. preparation method as claimed in claim 1, is characterized in that: in step (4), the weight ratio of calcium phosphate dibasic anhydrous prepared by tetracalcium phosphate and step (1) is 0.5-3: 1.
6. preparation method as claimed in claim 1, is characterized in that: in step (4), the particle diameter of tetracalcium phosphate is 0-20 μ m, purity >=99%.
7. preparation method as claimed in claim 1, is characterized in that: in step (4), solid-to-liquid ratio is 0.8g/ml.
8. preparation method as claimed in claim 1, is characterized in that: in step (4), the addition of porogen is 20% of solid phase weight.
9. preparation method as claimed in claim 1, is characterized in that: in step (4), in porogen, the mol ratio of mannitol and Poly(D,L-lactide-co-glycolide is 0.5-3: 1.
10. preparation method as claimed in claim 1, is characterized in that: in step (4), in porogen, the mol ratio of mannitol and Poly(D,L-lactide-co-glycolide is 2: 1.
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| CN106512086A (en) * | 2016-11-11 | 2017-03-22 | 江西理工大学 | Yttrium-doped calcium phosphate bone cement and preparation method thereof |
| CN109847095A (en) * | 2018-12-28 | 2019-06-07 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation of PEG cladding photosensitizer IR780 modified Injectable calcium-phosphate bone cement and product and application |
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Application publication date: 20140528 |