CN102526797A - Preparation method of high-strength biological glass bone bracket with regular-hole distribution - Google Patents
Preparation method of high-strength biological glass bone bracket with regular-hole distribution Download PDFInfo
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Abstract
The invention belongs to the technical field of the bioengineering, and particularly relates to a preparation method of a high-strength biological glass bone bracket with regular-hole distribution. The preparation method of the glass bracket with bioactivity and capability for complete degradation comprises the following steps of: using a fusion method to prepare borate bioactive glass, and crushing and sieving glass blocks into glass powder with certain size; mixing the glass powder body with organic mixed liquid propylene-glycol block polyether solution into uniform slurry; by the three-dimensional printing process of a computer, printing a bracket precursor (blank body) under a designed program; and after the blank body is dried, sintering the blank body under high temperature, and finally obtaining the glass bracket with excellent bioactivity.
Description
Technical field
The invention belongs to technical field of bioengineering, be specifically related to a kind of method for preparing of high strength bio-vitric bone support of regular pore size distribution.
Background technology
Support is built a structure as a kind of for the growth of cell temporarily, be can inducing cell differentiation bear the place with the similar histoorgan of support shape again, important effect is arranged in bone tissue engineer.The maximum characteristics of osseous tissue are that intercellular substance has one of tissue the hardest in a large amount of calcium deposition formation human bodies, and hydroxyapatite can be regarded the pressurized material as on the structure.For the timbering material in the bone tissue engineer, what primarily require is exactly mechanical property, and promptly the mechanical property of support must be complementary with the mechanical property of environmental organization: the support that intensity is low is not enough to support the daily routines demand of human body.The method for preparing at present support mainly contains foam impregnation method, pore creating material method, gas foaming method and heat and brings out phase separation method etc., for example at Chinese invention patent, among CN 101050053 B, has introduced the bone support of foam impregnation method preparation.These methods all attempt to build supporting structure by material structure itself, and the support intensity that is obtained by these traditional methods is generally on the low side, weight capacity can't with real bone photo coupling.Timbering material requires it must promote the regeneration of organizing on the other hand, and the ability of tissue regeneration can receive the influence of material conduction of interaction and support of character and the cell of material surface.
Receive increasing concern at a kind of novel osseous tissue material in the last few years, it is exactly a borate biological glass.It has good biological activity; Between bio-vitric, soft tissue and bone, exist close ion exchange; Thereby cause forming chemical bonding between material interface and the body bone tissue; The surface can generate the hydroxyapatite layer of biologically active, along with the prolongation of time can be degraded fully.But because the support intensity problem that the traditional preparation process method obtains, the bio-vitric support is difficult to use as the embedded material of weight bearing area.
Be based upon the basis (Chinese invention patent of the glass supporter preparation of existing a kind of controllable degradation property; CN 101050053 B and Chinese invention patent; CN 101125218 B) on, present patent application has been described bio-vitric high-strength bone support of a kind of regular pore size distribution and preparation method thereof, compares with process before; The support intensity that this patent is prepared improves an one magnitude, and has the characteristics of pore size distribution rule, connection.In this patent, stipulated the composition of borate biological glass supporter; The concrete implementation method of 3 D-printing technology; Print the method for preparing of slurry; Support cell experiment and zoopery have been carried out.The result shows this borate glass support crystallize not in sintering process, still keeps original glassy phase states of matter, has good processing properties; Owing to have uniform pore size distribution, all directions shrinkage degree is consistent during blank sintering, therefore can not change pore structure; Compare this support comprcssive strength improves with traditional method greatly; In addition, confirmed that through cell experiment and zoopery the bone tissue engineering scaffold of this method preparation has the performance of good bio-compatible, degradability and the growth of stimulation osteocyte.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing of high strength bio-vitric bone support of regular pore size distribution; Solve the problem that slurry can not adapt to quick shaping; Not high enough with the biological activity of the support of traditional method preparation, the perhaps not high enough shortcoming of comprcssive strength.
The method for preparing of the high strength bio-vitric bone support of the regular pore size distribution that the present invention proposes; Utilize the 3 D-printing technology that special borate biological glass paste is printed (extruding) and be piled into support presoma (green honeycomb body), sinter high strength bio-vitric support at last into regular pore structure.This support not only can be degraded in the physiology simulated solution gradually, and excellent biological compatibility and biological activity are arranged, and skeletonization is had stimulation; And higher mechanical properties is arranged, reparation has potential application to the segmental bone clinically.Concrete steps are following:
(1) preparation of glass powder
The bio-vitric that is used for support preparation is to be the borosilicate system glass of main body with the borate, the consisting of of bio-vitric powder: with B
2O
3Or P
2O
5Be glass network main body or the double SiO that contains
2Contain lime glass, total mol ratio is 30-90 mol%, the network outer body of glass contains CaO, and also contains Na
2O, K
2O alkali metal oxide and MgO, SrO alkaline earth oxide or rare-earth oxide; Total molar ratio of network-modifying ion oxide accounts for glass, and to form integral molar quantity be 5-80mol%, and wherein to account for integral molar quantity be 5-60mol% to the molar content of alkaline earth oxide; According to the composition and the proportioning of above-mentioned glass, get with the corresponding oxide of metallic oxide, chloride, carbonate, sulfate and the phosphatic raw material of industry as glass batch, mix homogeneously is at 1000-1400 ℃ of following melten glass and be incubated 0.5-8 hour; Quenching obtains glass blocks subsequently.With the gained glass blocks successively through the coarse crushing of horizontal type ball mill, planetary ball mill is in small, broken bits or jet mill is in small, broken bits, and screening obtains the glass powder that ultimate size is 0.05-50 μ m;
(2) preparation of the organic distiller liquor of propylene glycol block polyether
Propylene glycol block polyether is through nucleophilic substitution and synthetic by polyethers (molecular weight is 1800-2500) and DBPC 2,6 ditertiary butyl p cresol (purity is greater than 98%).The former molecular formula is HO. (C
2H
4O) m. (C
3H
6O) n.H, the latter are C
15H
24O.Both are mixed into the turbid liquid of suspension with the weight rate of 1:1-2.5:1,, dissolve this suspension, place there-necked flask with the toluene solution of 50wt%.With platinum chloric acid (H
2PtCl
66H
2O) aqueous isopropanol (concentration is 0.01mol/L) is as catalyst, and catalyst consumption is 50ug/g (catalyst weight/reactant weight), under 70-90 ℃ of temperature; High degree of agitation, condensing reflux, nitrogen protection; React after 5-8 hour, take out reactant, through distilling under reduced pressure; Remove monomer and low polymer, obtain heavy-gravity propylene glycol block polyether.With synthetic propylene glycol block polyether (gram), be dissolved in 50% ethanol (milliliter), ratio is that 1:0.5-1:1.5 makes solution, just obtains required organic distiller liquor.The phase transition temperature that characterizes organic distiller liquor with viscosimetry is between 20-40 ℃.Because the slurry that we need is the colloidal sol shape when low temperature, certain flowability is arranged, be higher than phase transition temperature and then solidify immediately.The phase transition temperature of this experiment helps controlling phase transformation and takes place near room temperature, and promptly this phase transition temperature helps synthetic support base substrate.
(3) preparation of glass slip
The glass powder of gained is mixed with above-mentioned distiller liquor with certain proportion, and blended ratio (is glass dust weight (gram): distiller liquor volume (milliliter)) be 1:0.1-1:0. 5; Be placed on through high degree of agitation 4-8 hour and deposit in 10 ℃ of-20 ℃ of water-baths, process uniform glass slip to remove bubble.It is for use after 4 hours to put into the refrigerator ageing at last.
(4) preparation of green honeycomb body
Earlier with the sieve of slurry with 10-225 μ m; The removal bulk is reunited; And the slurry after will sieving pours in notes (spray) love dart of printer, and slurry can be the adjustable notes of 0.2-2 millimeter (spray) love darts through the injection port diameter dimension, under 0.01-0.05MPa pressure, extrudes from injection port (shower nozzle); Extruded velocity is the 0.05-1.0 mm/second, constitutes the slurry post that becomes wire continuously.Jet pipe and the slip extruded all are arranged in 40 ℃-70 ℃ oil bath (99% kerosene) in the print procedure; So that the slip that prints can be solidified into solid column rapidly; So not only can guarantee the base substrate regular shape that prints, can also bear the weight that adds solid column on it subsequently immediately.The ground floor slip that squeezes out is tiled in Al
2O
3On the plate, slip subsequently is accumulation successively from bottom to top, is solidified into the green honeycomb body that is made up of solid column.The body preparation process designs by computer program in advance, and the omnidistance speed of extruding slurry of controlling, to adapt to the setting time of slip bonding lower floor solid column; The position that omnidistance control is extruded, with regulate by solid column forms about, about and three-dimensional pore space just, constitute the different porositys and the green honeycomb body in aperture.
(5) sintering of green honeycomb body
The support base substrate is put into 10-90 ℃ baking oven insulation earlier and was removed most of kerosene in 12-48 hour.Put into Muffle furnace then and come unstuck and sintering, its sintering condition is: be raised to 400-550 ℃ with 1 ℃/min programming rate, be incubated 5-24 hour; Be raised to 550-700 ℃ with 1 ℃/min programming rate, be incubated 1-5 hour.
Utilize institute of the present invention acquisition support can be applied to the reparation of sections property bone, can be as bone holder material in the bone tissue engineer, can degrade fully forms new bone.
The glass supporter that utilizes the inventive method to prepare has better biocompatibility, can stick osteoblast; Better biological activity is arranged, can transform the inorganic constituents hydroxyapatite of skeletonization after the glass supporter degraded; Excellent biodegradability is arranged, in vivo degraded fully.Gained glass supporter hole rule, porosity is 10-95%, and the maximum diameter of hole is of a size of 10-1000 μ m, and comprcssive strength is 30-70 MPa, and the support comprcssive strength that generally obtains than the traditional method preparation is high.And because 3 D-printing method itself is to extrude slurry according to the three-dimensional profile software that has designed in advance, also just can preset meter, satisfy the needs that the different parts bone is repaired the structure and the performance of support.
Description of drawings
Fig. 1 is support all directions shape appearance figures: (a) axonometric chart, (b) vertical view, (c) side view.
Fig. 2 is that the phase transition temperature of propylene glycol block polyether is measured.
Fig. 3 is a support comprcssive strength curve.
Fig. 4 is the thing XRD determining mutually of glass dust and preparation after-poppet.
Fig. 5 is the XRD figure spectrum of support sample immersion after 20 days.
Fig. 6 is the FTIR collection of illustrative plates of support sample immersion after 20 days.
Fig. 7 be osteoblast MC3T3-E1 under 37 ℃ of conditions in support pattern and the cell adhesion situation on it.Wherein: (a) soak 3 days after-poppet patterns, (b) cell adhesion after 5 days, (c) cell adhesion after 9 days.
Fig. 8 implements to imbed the X ray sheet after support is tested for segmental bone defect.(a) 4 weeks, (b) 8 weeks, (c) 12 weeks.
The specific embodiment
Further specify the present invention through embodiment below.
Embodiment 1:The preparation of three-dimensional communication support is made up of following five steps.
(1) preparation of glass powder
Take by weighing the 3.8185g natrium carbonicum calcinatum, 9.9587g Anhydrous potassium carbonate, 1.7502g basic magnesium carbonate, 19.8328g calcium carbonate, 7.9781g strontium carbonate, 9.7420g silicon dioxide, 41.2991g boric acid, 5.6206g sodium dihydrogen phosphate.After mix homogeneously and the grinding batching is placed inherent 1200 ℃ of insulation 30 min of platinum crucible; Subsequently the vitreous humour that obtains is watered that quenching obtains glass blocks on steel plate.With the gained glass blocks successively through the coarse crushing of horizontal type ball mill, ball milling is in small, broken bits and sieve and obtain the glass powder that ultimate size is 0.05-5 μ m.
(2) mensuration of the preparation of the organic distiller liquor of propylene glycol block polyether and phase transition temperature
Get the toluene solution (50wt%) of 50ml, place there-necked flask.Take by weighing polypropylene glycol ether (molecular weight is 2200) 15 grams again, other takes by weighing DBPC 2,6 ditertiary butyl p cresol (purity is greater than 98%) 10 grams, and both fully are mixed into uniform suspension, are added drop-wise in the there-necked flask.Get platinum chloric acid (H again
2PtCl
66H
2O) 1.25 milligrams of aqueous isopropanols (concentration is 0.01mol/L) as catalyst, are added drop-wise in the there-necked flask.Under 90 ℃ of temperature, high degree of agitation, condensing reflux, nitrogen protection was reacted after 5 hours, took out reactant, through distilling under reduced pressure, obtained heavy-gravity propylene glycol block polyether.
Heavy-gravity propylene glycol block polyether with 30 milliliter of 50% dissolve with ethanol, is obtained required organic distiller liquor.Characterize the viscosity catastrophe point of organic distiller liquor under different temperatures with viscosimetry, confirm that phase transition temperature is 27 ℃ of (see figure 2)s.
(3) preparation of glass slip
Take by weighing the above-mentioned glass dust of 5g, add the organic distiller liquor solution of 2 ml, place beaker to stir, glass powder is dispersed in the blending liquid solution.And then be placed in 10 ℃ of water-baths and remove bubble, process uniform slip, be put in 4 ℃ of refrigerators, cold preservation was used after 12 hours.
(4) preparation of green honeycomb body
With the sieve of slip, remove bulk and reunite earlier, then the slip that sieves is put into the three-dimensional printer needle tubing with 75 μ m.Needle tubing and the slip extruded all are arranged in 40 ℃ oil bath (99% kerosene) in the print procedure.Put into Al in the oil bath pan
2O
3Plate is placed at Al with printing head
2O
3On the plate, open the computer printout program, the printer spout is extruded green honeycomb body and is deposited in Al
2O
3On the plate.
(5) sintering of green honeycomb body
The baking oven insulation that green honeycomb body is put into 30 ℃ was removed most of kerosene in 24 hours, put into then that Muffle furnace comes unstuck and sintering, and its sintering schedule is: be raised to 500 ℃ with 1 ℃/min programming rate, be incubated 12 hours; Be raised to 600 ℃ with 1 ℃/min programming rate, be incubated 1 hour, powered-down then, after 24 hours, furnace temperature is reduced to room temperature, and green honeycomb body is sintered into support.
Through above-mentioned each step, be prepared into high strength bio-vitric support (seeing Figure 1A, 1B and 1C) with regular pore structure.
Embodiment 2:The mensuration of the aperture of support, measurement method of porosity and intensity
By the method that embodiment 1 is narrated, preparation three-dimensional communication support.With reference to national standard GB 5164-1985 " mensuration of permeable sintered metal materials percent opening ", the porosity of support is measured, the result shows that this brace aperture rate is 60%, the maximum diameter of hole is of a size of 400 μ m, is consistent with the observation of the SEM of Figure 1B and C.The support comprcssive strength of utilizing the compressive strength determination appearance to record among the embodiment 1 is the 30MPa (see figure 3).
Embodiment 3: the mensuration of biological property:
By the method that embodiment 1 is narrated, preparation three-dimensional communication support.The support that makes is carried out the test of biological activity, biological degradability and biocompatibility.
Support to making is made XRD analysis, and with the glass dust (see figure 4) of making comparisons, explain that the support of acquisition still is a glassy phase through a series of hot-working.Then this support, temperature is made immersion test in being 37 ℃ physiology simulated solution; Take out support after 20 days; Through XRD and FTIR course of reaction and reaction afterproduct are characterized (seeing Fig. 5 and 6); Product X RD spectrum is shown as the collection of illustrative plates of typical hydroxyapatite crystal, and the FTIR spectrum of product is shown as the infared spectrum of typical hydroxyapatite.The result shows: this borate glass bioactive bracket sample can be converted into strontium containing hydroxyapatite in the reaction of external biological mineralising, have good biological activity and degradability.
For support and osteoblastic biocompatibility and the cell adhesion property of investigating preparation; The support that makes is put into the culture dish that fills MC3T3-E1 osteoblast culture fluid cultivate 3 respectively; 5 and 9 days; Take out support, after fixing with glutaraldehyde, put into the ethanol collection again and remove moisture and lyophilization.SEM shows that the glutinous (see figure 7) of creeping of a large amount of cells is arranged on the support, and explaining that this support is fine has biocompatibility and a cell adhesion property.
Embodiment 4: the zoopery of support:
By the method that embodiment 1 is narrated, preparation three-dimensional communication support.Support to making carries out zooperal test.
It is damaged that 15mm segmental bone is processed in the bilateral radius stage casing of new zealand white rabbit, imbeds the support of embodiment 1 preparation, and Fig. 8 is a segmental bone extirpation experiment X ray sheet.Postoperative 4,8,12 weeks took the photograph sheet through X ray and observe the osteogenesis situation, can find out, implanted 4 all after-poppet materials and bone and directly combined; 8 all after-poppet density of material reduce, and material two ends and bone merge basically; 12 all backs materials are degraded fully, osteogenesis is obvious, the moulding basic completion of bone.Explain that the support that makes has a good repair to the bone of animal is damaged.
Claims (3)
1. the method for preparing of the high strength bio-vitric bone support of a regular pore size distribution is characterized in that concrete steps are following:
(1) preparation of glass powder
The bio-vitric that is used for support preparation is to be the borosilicate system glass of main body with the borate, the consisting of of bio-vitric powder: with B
2O
3Or P
2O
5Be glass network main body or the double SiO that contains
2Contain lime glass, total mol ratio is 30-90 mol%, the network outer body of glass contains CaO, and also contains Na
2O, K
2O alkali metal oxide and MgO, SrO alkaline earth oxide or rare-earth oxide; Total molar ratio of network-modifying ion oxide accounts for glass, and to form integral molar quantity be 5-80mol%, and wherein to account for integral molar quantity be 5-60mol% to the molar content of alkaline earth oxide; According to the composition and the proportioning of above-mentioned glass, get with the corresponding oxide of metallic oxide, chloride, carbonate, sulfate and the phosphatic raw material of industry as glass batch, mix homogeneously is at 1000-1400 ℃ of following melten glass and be incubated 0.5-8 hour; Quenching obtains glass blocks subsequently; With the gained glass blocks successively through the coarse crushing of horizontal type ball mill, planetary ball mill is in small, broken bits or jet mill is in small, broken bits, and screening obtains the glass powder that ultimate size is 0.05-50 μ m;
(2) preparation of the organic distiller liquor of propylene glycol block polyether
Being 1800-2500 polyethers and DBPC 2,6 ditertiary butyl p cresol with molecular weight is mixed into the turbid liquid of suspension with the weight rate of 1:1-2.5:1, with the toluene solution of 50wt%, dissolves this suspension, places there-necked flask; As catalyst, catalyst consumption is 50ug in every gram reactant, under 70-90 ℃ of temperature with the aqueous isopropanol of platinum chloric acid; Stir condensing reflux, nitrogen protection; React after 5-8 hour, take out reactant, through distilling under reduced pressure; Remove monomer and low polymer, obtain heavy-gravity propylene glycol block polyether; With synthetic propylene glycol block polyether (gram), be dissolved in 50% ethanol (milliliter), ratio is that 1:0.5-1:1.5 makes solution, just obtains required organic distiller liquor; The phase transition temperature that characterizes organic distiller liquor with viscosimetry is between 20-40 ℃;
(3) preparation of glass slip
The glass powder of step (1) gained is mixed glass dust weight (gram) with the organic distiller liquor of step (2) gained: distiller liquor volume (milliliter) is 1:0.1-1:0. 5; Deposit in 10 ℃ of-20 ℃ of water-baths to remove bubble through stirring to be placed in 4-8 hour, process uniform glass slip; Put into the refrigerator ageing, for use;
(4) preparation of green honeycomb body
Earlier with the sieve of step (3) gained glass slip with 10-225 μ m; The removal bulk is reunited; And the slurry after will sieving pours in the syringe of printer, and slurry is the adjustable syringe of 0.2-2 millimeter through the injection port diameter dimension, under 0.01-0.05MPa pressure, extrudes from injection port; Extruded velocity is the 0.05-1.0 mm/second, constitutes the slurry post that becomes wire continuously; Jet pipe and the slip extruded all are arranged in 40 ℃-70 ℃ oil bath in the print procedure, and the ground floor slip that squeezes out is tiled in Al
2O
3On the plate, slip subsequently is accumulation successively from bottom to top, is solidified into the green honeycomb body that is made up of solid column; The body preparation process designs by computer program in advance, and the omnidistance speed of extruding slurry of controlling, to adapt to the setting time of slip bonding lower floor solid column; The position that omnidistance control is extruded, with regulate by solid column forms about, about and three-dimensional pore space just, constitute the different porositys and the green honeycomb body in aperture;
(5) sintering of green honeycomb body
The support base substrate is put into 10-90 ℃ baking oven insulation earlier and was removed most of kerosene in 12-48 hour; Put into Muffle furnace then and come unstuck and sintering, its sintering condition is: be raised to 400-550 ℃ with 1 ℃/min programming rate, be incubated 5-24 hour; Be raised to 550-700 ℃ with 1 ℃/min programming rate, be incubated 1-5 hour.
2. method according to claim 1 is characterized in that gained glass supporter hole rule, and porosity is 10-95%, and the maximum diameter of hole is of a size of 10-1000 μ m, and comprcssive strength is 30-70 Mpa.
3. according to the method described in the claim 1, it is characterized in that the gained support can be applied to the reparation of sections property bone, can be as bone holder material in the bone tissue engineer, can degrade fully forms new bone.
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