CN103830774B - A kind of bone cement and preparation method thereof - Google Patents
A kind of bone cement and preparation method thereof Download PDFInfo
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- CN103830774B CN103830774B CN201410077683.0A CN201410077683A CN103830774B CN 103830774 B CN103830774 B CN 103830774B CN 201410077683 A CN201410077683 A CN 201410077683A CN 103830774 B CN103830774 B CN 103830774B
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Abstract
The present invention relates to a kind of Bone Colonizable Cements In Rabbits and preparation method thereof, described Bone Colonizable Cements In Rabbits is made up of the component of following weight percentage: 45-78wt% magnesium oxide; 20-50wt% ammonium phosphate salt; 0.5-10wt% retarder; 0.01-10wt% magnesium powder; And consolidation liquid, the liquid-solid ratio of described consolidation liquid and the mixture of above-mentioned material is 0.06-1.0ml/g.The present invention by adding metal magnesium powder in ammonium phosphate salt and magnesian system, thus acceleration system generation ammonia realizes pore-creating.Preparation technology's simple and fast of the present invention, adopts the loose structure that method of the present invention obtains, and pore size is even, porosity is large, is conducive to cell adsorption and creeps, and can promote the growth of osteocyte.Bone Colonizable Cements In Rabbits of the present invention has good mechanical property, biocompatibility and degradability, can be widely used in field of medical materials.
Description
Technical field
The invention belongs to biomedical materials field, relate to a kind of Bone Colonizable Cements In Rabbits and preparation method thereof, more particularly, relate to a kind of porous, degradable magnesium phosphate cement containing metal magnesium powder and preparation method thereof.
Background technology
Magnesium phosphate cement (Magnesium Phosphate Bone Cement, MPC) is as the research of biomaterial, and report is main is both at home and abroad used as tooth cement, artificial joint binding agent, bone stabilizing agent etc.Magnesium phosphate cement has obtained the favorable comment of numerous experts and scholars due to its biocompatibility and biological activity, is considered to one of the Bone Defect Repari and substitution material of current most potentiality.Non-toxic reaction, good biocompatibility in animal body implanted by this material, progressively absorbed, promote the growth of osteocyte, guide new Bone Ingrowth after solidification with sclerotin compact siro spinning technology, after implanting material degradation and new bone formation reciprocity.
MPC bone cement has the characteristic fast solidifying, early anti pressured intension is high compared with traditional calcium phosphate bone cement, plasticity and adhesivity good, volume microdilatancy during solidification, and material non-toxic.Its implantation can not cause the significant change of animal body metaboilic level, can degradation in vivo, and hydrated product is made a living ores ammonium magnesium phosphate one by one, and biocompatibility is higher, be therefore expected to comminuted fracture and artificial limb inlay fixing in obtain extensive use.In May, 2009, U.S. FDA have approved a kind of a kind of new type bone repair materials list marketing of being developed by Bone Solutions company of the U.S., this product is awarded 2009 annual North America technical control Grand Prixs, by praise for opening brand-new field, one, bone collection market.
But the overwhelming majority in MPC bone cement product common is not in the market loose structure.Research shows, osseous tissue is loose structure, so the bone renovating material of porous is more conducive to Bone Defect Repari process.This is because porous material can provide the three dimensions of existence for cell, be conducive to cell adhesion and growth, be conducive to the formation of extracellular matrix, be conducive to the transmission of oxygen and nutrient substance, be conducive to the discharge of metabolite, also help blood vessel and neural growing into simultaneously, promote the process of reconstruction of bone.
But also not all porous material is all suitable for as bone tissue engineering stent material.Generally will obtain the embedded material of perfect in shape and function, minimum-value aperture requires that this is the basic demand of bone guided for 100-250 μm.The pertusate bone cement material of tool, cell can be allowed easily to attach for its rough external surface and inner void can provide space allow Growth of Cells.The grow into desirable aperture of artificial material of osseous tissue is 100-500 μm.Therefore, the porous bone cement aperture made at present is 100-500 μm.Usually, aperture be less than 5 μm be called micropore.The bone cement of dense form only has micropore, and the existing micropore of the bone cement of porous type also has macropore (100-500 μm), micropore to increase material and interstitial fluid contacts area, is conducive to biodegradation, but macropore is more conducive to osseous tissue grows into.
At present, the preparation method of conventional porous bone cement has multiple, mainly contains that particle stripping is sent out, microsphere pore-creating is sent out, foaming etc.Such as, patent CN101076344A discloses a kind of multi-purpose bio-material composition, comprises: KH
2p0
4, metal-oxide (that is, MgO), calcium containing compound, sugar and water.Patent CN102552986A discloses a kind of method that metal porogen prepares porous bone cement, in molar ratio for the ratio of 1:1 takes β-TCP and Ca (H
2pO
4)
2make composite granule after H2O powder mull, the citric acid solution adding 0.5mol/L is wherein in harmonious proportion, and then adds metal dust wherein, its natural foaming is solidified, obtains porous bone cement material.Authorization Notice No. is the preparation method and application that the Chinese patent of CN1193614A discloses a kind of porous calcium phosphate bone cement containing pore former, and it mainly through adding nontoxic slightly soluble salt, acid salt and basic salt or nontoxic surfactant obtains porous calcium phosphate bone cement as pore former in calcium phosphate bone cement.Disclose one in patent CN102989042 to be solid blowing agent with carbonate, to take sulfate as curing accelerator, chitosan and hydroxypropyl emthylcellulose are bi-component cross-linking agent, prepare injectivity porous bone cement of solidification, anti-collapsibility soon and preparation method thereof.Its setting time of injectivity porous bone cement that the method is prepared is at 5-25min, and meet water after solidification 20min-2h not defeated and dispersed, cured product has the linked hole of 100-1000 μm, and porosity is 1-70%, and comprcssive strength is between 0.5-40MPa.A kind of Absorbable rod macromolecule that adds is disclosed to obtain the method that aperture is the porous bone cement of 150-300 μm in patent CN102113965A.But the porous bone cement that said method is prepared all exists certain weak point: first, and Recipe is comparatively complicated, often need to add some adjuvants, and adjuvant is difficult to remove completely; Secondly, its degradation time is difficult to match with cell growth cycle, makes cell be difficult to grow into wherein, is difficult to accomplish the end in view; Again, the micropore size obtained differs, the porosity that very difficult acquisition is comparatively stable; Biological degradability is poor.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of Bone Colonizable Cements In Rabbits and preparation method thereof, this Bone Colonizable Cements In Rabbits is the magnesium phosphate cement of porous, degradable.The magnesium phosphate cement of this porous, degradable mainly by adding metal magnesium powder in ammonium phosphate salt and magnesian system, thus acceleration system generation ammonia realizes pore-creating.
Research shows that magnesium can participate in a series of metabolic processes in body, and being also the main component of composition bone, is the necessary element of osteogenesis.First, magnesium ion can promote the deposition of calcium, and then promotes the growth of new bone tissue; Secondly, magnesium ion can promote osteoblast in the adhesion of implantation material surface and improve Integrated implant ability; Again, implant the speed can accelerating callus distraction osteogenesis in early days, promote the maturation of sclerotin and the performance of function; The magnesium ion of last high concentration can improve osteoblastic activity.In addition, magnesium metal also has lower elastic modelling quantity and suitable intensity except having above-mentioned advantage, the performances such as good biocompatibility, biodegradability and absorbability.
Reaction mechanism of the present invention is as follows:
Before not adding metal magnesium powder, in ammonium phosphate salt and magnesian system, following three reactions of main generation, have a large amount of ammonia to produce, thus realize pore-creating object in system.
MgO+H
2O→Mg
2++2OH
-(2)
After adding metal magnesium powder, there are (4) and (5) two reactions, wherein react the ammonia that (5) produce, accelerate pore-creating further.By
consumption, accelerate the carrying out of reaction (1), simultaneously due to OH that reaction (4) produces
-more, accelerate again the carrying out of reaction (3), owing to reacting the existence of (3) and (5), the generating rate of ammonia is accelerated, thus the factor of created gase of system is accelerated, and finally realizes pore-creating simultaneously.But, because the water content in system is effectively controlled, so reaction (4) can not continue to carry out, when system is solidified, reaction (4) also will stop, so the hydrogen produced in system is very little, final metal magnesium powder is still present in system with the form of metal dust, thus realizes the interpolation of pore-creating and metal magnesium powder simultaneously.
NH
3·H
2O→NH
3↑+H
2O (5)
An object of the present invention is to be achieved through the following technical solutions:
A kind of Bone Colonizable Cements In Rabbits, is made up of the component of following weight percentage:
Magnesium oxide 45-78wt%
Ammonium phosphate salt 20-50wt%
Retarder 0.5-10wt%
Magnesium powder 0.01-10wt%, and
Consolidation liquid, the liquid-solid ratio of described consolidation liquid and the mixture of above-mentioned material is 0.06-1.0ml/g.In order to the bone cement obtained has excellent viscosity and injectable type energy, the present invention found through experiments in liquid-solid ratio when 0.06-1.0ml/g is interval, and the sample combination property obtained is more excellent.
Object of the present invention can also be realized further by following technical scheme:
Preferably, described ammonium phosphate salt is one in Ammonium biphosphate, diammonium phosphate, ammonium phosphate or its mixture; Described retarder is boric acid or borate.
Preferably, the granularity of described magnesium oxide, described ammonium phosphate salt, described retarder and described magnesium powder is 10 μm-80 μm.Preferred, the granularity of described magnesium oxide, described ammonium phosphate salt, described retarder and described magnesium powder is 20 μm-50 μm.
Preferably, the percentage by weight of described magnesium powder is between 0.01-0.6wt%, preferred, and the percentage by weight of described magnesium powder is between 0.02-0.3wt%.
Preferably, described liquid-solid ratio is 0.1-0.25ml/g.
Preferably, described magnesium oxide calcines 3-6 hour at temperature 1500 DEG C-1700 DEG C.
Another object of the present invention is achieved through the following technical solutions:
A preparation method for Bone Colonizable Cements In Rabbits, comprises the following steps:
Step one gets all the raw material ready by following composition proportion (percentage by weight wt%):
Magnesium oxide 45-78%
Ammonium phosphate salt 20-50%
Retarder 0.5-10%
Magnesium powder 0.01-10%%
The ratio of step 2 in 0.06-1.0ml/g in the mixture of said components adds consolidation liquid, mix homogeneously, pours natural molding in mould into.
Another object of the present invention can also be realized further by following technical scheme:
Preferably, described ammonium phosphate salt is one in Ammonium biphosphate, diammonium phosphate, ammonium phosphate or its mixture; Described retarder is boric acid or borate.
Preferably, the granularity of described magnesium oxide, described ammonium phosphate salt, described retarder and described magnesium powder is 10 μm-80 μm.Preferred, the granularity of described magnesium oxide, described ammonium phosphate salt, described retarder and described magnesium powder is 20 μm-50 μm.
Preferably, the percentage by weight of described magnesium powder is between 0.01-0.6wt%, preferred, and the percentage by weight of described magnesium powder is between 0.02-0.3wt%.
Preferably, the ratio adding described consolidation liquid is 0.1-0.25ml/g.
Preferably, described magnesium oxide calcines 3-6 hour at temperature 1500 DEG C-1700 DEG C.
Compared with prior art, a kind of Bone Colonizable Cements In Rabbits disclosed by the invention and preparation method thereof, tool has the following advantages:
1) in ammonium phosphate salt and magnesian system, metal magnesium powder is added.Magnesium metal is as a kind of catalyst in system, and the system that accelerates produces ammonia thus realize even pore-creating, and the magnesium metal after completing pore-creating in system is still comparatively complete to be present in system.
2) the loose structure pore size that the Bone Colonizable Cements In Rabbits adopting method of the present invention to prepare obtains evenly (aperture is at 100-500 μm), porosity large (60%+20%) is conducive to cell adsorption and creeps, the growth of osteocyte can be promoted, improve the biocompatibility of material.
3) Bone Colonizable Cements In Rabbits of the present invention has good mechanical property, biocompatibility and degradability.
4) preparation technology's simple and fast of the present invention, field of medical materials can be widely used in, particularly Bone Colonizable Cements In Rabbits of the present invention can be made with medicine, cell or somatomedin compound and have bone growth and promote and treat and the bio-medical reparation of the function such as osteocyte fast breeding or packing material, is particularly useful for the fields such as orthopaedics, dentistry and orthopedics.
5) as Bone Defect Repari or alternate material, the Bone Colonizable Cements In Rabbits prepared by the present invention is the magnesium phosphate cement possessing loose structure, has more advantages and larger potentiality compared with conventional phosphoric acid magnesium bone cement.Porous calcium phosphate magnesium bone cement not only has excellent biocompatibility and biological activity as timbering material, and can be repopulating cell larger adhesive face and enough growing spaces are provided, promote cell adhesion, propagation and differentiation, induction osseous tissue is formed fast, guiding blood vessel, nervous tissue inwardly grow and pass, discharge for the nutrition exchange of freshman bone tissue and refuse and passage is provided, also add the contact area of material and hard and soft tissue, be conducive to fully contacting with body fluid, accelerate the degraded of material.In addition, porous calcium phosphate magnesium bone cement can also as the carrier of medicine, various somatomedin, gene isoreactivity material.
Accompanying drawing explanation
Fig. 1 is common MPC and the MPC bone cement exotherm mixing magnesium metal.
Fig. 2 is the SEM picture of MPC bone cement sample surfaces, and wherein Fig. 2 a is the SEM picture of the MPC bone cement sample surfaces not mixing metal magnesium powder; Fig. 2 b is for mixing the SEM picture of the MPC bone cement sample surfaces prepared by metal magnesium powder.
Fig. 3 is common MPC bone cement and the MPC bone cement mixing metal magnesium powder XRD figure spectrum before the reaction.Fig. 3 a composes with the XRD figure of the MPC bone cement sample do not mixed prepared by metal magnesium powder for mixing metal magnesium powder; Fig. 3 b is the XRD figure spectrum that Fig. 3 a sample soaks sample after 7 days in simulated body fluid.
Fig. 4 shows the mechanical property contrast of the MPC-Mg bone cement sample prepared by the different formulations of embodiments of the invention 2-7.
Detailed description of the invention:
Describe below by specific embodiment, set forth substantive distinguishing features of the present invention and marked improvement further, but the present invention is only confined to embodiment by no means.
Prepared by raw material:
Magnesium oxide powder is the important component in mixture of the present invention.The optional existing product (pharmaceutical grade or AR level) on the market of magnesium oxide obtains through calcination process.According to required final characteristic sum setting time, select different calcine technologies.Calcine technology is chosen as in the present invention: calcining heat prioritizing selection 1500 DEG C-1700 DEG C, and continues 3-6 hour.After calcining, magnesium oxide powder is mixed with ammonium phosphate salt, retarder (boric acid or sodium tetraborate).Various powder is carried out classification and homogenize (such as by vibratory milling or mortar grinder) in advance before mixing, make their granularity be 10 μm-80 μm.In solid constituent of the present invention, in order to make the performance of product more excellent, the granule in size range is no less than 90%, the granule that the higher limit of the granularity preferably not more than 5% is greater than 80 μm.
When powder sample upon mixing mixes with consolidation liquid, usually select liquid-solid ratio to be 0.06-1.0ml/g, the addition of consolidation liquid also can be regulated as required to form the bone cement of different viscosities.Described consolidation liquid comprises deionized water, pure water, normal saline, blood plasma acid phosphate, Quadrafos dilution, magnesium chloride solution etc.According to condition, can by artificial or electric stirring 3-5 minute by slurry.Can be poured in mould after sample mix is even and be cured.In order to simulate the environment after implant into body in vitro, its sample being placed in 37 DEG C, being cured in the environment of the constant temperature and humidity of 100% humidity.Take out after sample solidifies completely, carry out the test of the correlated performance such as resistance to compression, bending resistance.
In order to determine the biological activity of the porous material that the present invention obtains and assess its degradability, the method that the human body simulation body fluid that we adopt soaks (SBF solution) is determined.Its specific practice is: 0.5g porous material is immersed in 100ml SBF solution.Tested the degradability of magnesium metal by the XRD of test reaction product, assess the biodegradability of its this material with this.SBF contains the ion identical with human plasma and ion cluster concentration.Shown in its concrete table composed as follows:
Embodiment 1:
Take the magnesium oxide powder 2.7g of particle diameter 10 μm-80 μm, Ammonium biphosphate powder body 2.15g, sodium tetraborate powder body 0.15g.By even for above-mentioned three kinds of powder body grinding distribution in mortar, add 0.4ml normal saline, reconcile into even walk with dentistry modulation cutter, then put into 37 DEG C, 100% humidity environment solidification 2 hours, firming body intensity is good.
Embodiment 2:
Take the magnesium oxide powder 2.585g (51.7%) of particle diameter 30 μm-50 μm, Ammonium biphosphate powder body 2.355g (47.1%), boric acid powder body 0.059g (1.18%), metal magnesium powder 0.001g (0.02%).By even for powder body grinding distribution in mortar in above-mentioned four, add 3ml magnesium chloride solution, even walk is reconciled into dentistry modulation cutter, then 37 DEG C of 100% humidity environment solidification 2 hours is put into, by microscopic examination, sample even aperture distribution, pore size is about 250+20 μm, porosity is 75%, and comprcssive strength is about 8.8MPa.Fig. 1 shows the common MPC prepared according to embodiment 1 and its exothermic heat of reaction temperature curve of MPC-Mg bone cement prepared according to embodiment 2.As can be seen from Figure 1, with common MPC bone cement exothermic phase ratio: first, mix its exothermic temperature of MPC bone cement of metal magnesium powder a little more than the former, but exothermic temperature still maintains reduced levels (~ 55 DEG C).This exothermic temperature scope had both been conducive to solidifying of bone cement, also have certain bactericidal action, the heat discharged in its solidify reaction process effectively can kill the harmful levels of pathogens of filling around tissue within the specific limits also can not cause serious burning to autologous tissue simultaneously simultaneously.Secondly, the time reaching heat release maximum is short, and the setting time that metal magnesium powder can shorten bone cement is mixed in this explanation, and this feature can shorten the operating time of doctor in Clinical practice, accelerates procedure, improves procedure efficiency.
Mix magnesium powder for the impact of MPC bone cement structure and the assessment to metal magnesium powder pore-creating performance to represent comparatively intuitively, the microscopic appearance mixing magnesium MPC bone cement and common MPC bone cement has been done one and has contrasted (as shown in Figure 2) by the present invention.Fig. 2 a is the SEM picture of the common MPC bone cement according to embodiment 1 preparation.Can be found out the common MPC bone cement not mixing magnesium powder by Fig. 2 a, its surface texture is comparatively fine and close, has micro-crack and minority pore to exist.Fig. 2 b is the SEM picture of porous MPC bone cement of the interpolation metal magnesium powder prepared according to embodiment 2.Can find out after mixing the metal magnesium powder of 0.02wt% by Fig. 2 b, its structure just there occurs obvious change, loose and porous structure is become by compact texture originally, compared with the micropore in Fig. 2 a, the attachment existing for osteocyte of the porous shown in Fig. 2 b and adhesion provide good growing environment, be conducive to growth and the increment of osteocyte, this will be conducive to the generation of osseous tissue, thus the speed of growth of accelerated bone and healing rate.This evidence shows that adding metal magnesium powder can promote that magnesium phosphate cement forms the structure of porous.
What Fig. 3 represented is that common MPC bone cement is composed with the XRD figure that the MPC bone cement mixing metal magnesium powder simulates mineralising 7 days front and back in vitro.Wherein mix magnesium before Fig. 3 a display reaction to compose with the MPC bone cement XRD figure of not mixing magnesium, therefrom can find out the characteristic peak (square labelling) of obvious magnesium metal, prove that magnesium metal has successfully mixed in MPC bone cement.Fig. 3 b represents that the MPC bone cement containing magnesium soaks the spectrum of the XRD figure after 7 days in simulated body fluid, therefrom can find out, soak after 7 days and still have the characteristic peak of stronger magnesium metal to occur in simulated body fluid.This phenomenon shows: 1) successfully prepare the MPC bone cement containing metal magnesium powder early stage; 2) in simulated body fluid, the characteristic peak of immersion magnesium after 7 days has certain weakening before comparing, such as, in Fig. 3 b, the characteristic peak intensity of the magnesium at 48 ° of places is reduced to 56.06cps (MPC-Mg-7d) from the 403.6cps (MPC-Mg) before immersion, this illustrates that the magnesium metal mixed has started degraded, but the speed of degraded is slower, this characteristic an object of the present invention just, introducing has bioactive magnesium metal element, slowly can degrade the object reaching the growth promoting osteocyte after implanting; 3) demonstrate the correctness of above-mentioned reaction mechanism simultaneously.
Embodiment 3:
Take magnesium oxide powder 3.12g (60.89%), diammonium phosphate powder body 1.804g (35.2%) that particle diameter is 60 μm-80 μm, sodium tetraborate powder body 0.03g (0.59%), metal magnesium powder 0.17g (3.32%).By even for powder body grinding distribution in mortar in above-mentioned four, add 2ml deionized water solution, even walk is reconciled into dentistry modulation cutter, then 370 (2100% humidity environment solidifications 2 hours are put into, by microscopic examination, sample even aperture distribution, pore size is about 150+20 μm, porosity 55%, comprcssive strength is about 4.5MPa.
Embodiment 4:
Take the magnesium oxide powder 3.9g (78%) that particle diameter is 10 μm-30 μm, diammonium phosphate powder body 1g (20%), boric acid powder body 0.07g (1.4%), metal magnesium powder 0.03g (0.6%).By even for powder body grinding distribution in mortar in above-mentioned four, add 0.5m1 normal saline, even walk is reconciled into dentistry modulation cutter, then 37 DEG C of 100% humidity environment solidification 2 hours is put into, by microscopic examination, sample even aperture distribution, pore size is about 350+20 μm, porosity 65%, comprcssive strength is about 6.2MPa.
Embodiment 5:
Take the magnesium oxide powder 2.5g (50%) that particle diameter is 40 μm-60 μm, Ammonium biphosphate powder body 2.1g (42%), sodium tetraborate powder body 0.1g (2%), metal magnesium powder 0.3g (6%).By even for powder body grinding distribution in mortar in above-mentioned four, add 4ml ammonium dibasic phosphate solution, even walk is reconciled into dentistry modulation cutter, then 37 DEG C of 100% humidity environment solidification 2 hours is put into, by microscopic examination, sample even aperture distribution, pore size is about 220 ± 20 μm, porosity 60%, after measured the powder of the present embodiment and consolidation liquid be in harmonious proportion after hardening time be about 13 minutes, comprcssive strength is 4.6MPa.
Embodiment 6:
Take the magnesium oxide powder 3g (60%) that particle diameter is 70 μm-80 μm, Ammonium biphosphate powder body 1.42g (28.4%), sodium tetraborate powder body 0.475g (9.5%), metal magnesium powder 0.105g (2.1%).By even for powder body grinding distribution in mortar in above-mentioned four, add 1.2ml deionized water, even walk is reconciled into dentistry modulation cutter, then put into 37 DEG C of 100% humidity environment solidification 2 hours, detect with stereomicroscope, sample even aperture distribution, pore size is about 200 ± 20 μm, porosity 80%, after measured the powder of the present embodiment and consolidation liquid be in harmonious proportion after hardening time be about 7 minutes, comprcssive strength is 5.2MPa.
Embodiment 7:
Take the magnesium oxide powder 2.25g (45%) that particle diameter is 30 μm-40 μm, Ammonium biphosphate powder body 2.05g (41%), sodium tetraborate powder body 0.2g (4%), metal magnesium powder 0.5g (10%).By even for above-mentioned four kinds of powder body grinding distribution in mortar, add 2.5ml deionized water, even walk is reconciled into dentistry modulation cutter, then put into 37 DEG C of 100% humidity environment solidification 2 hours, detect with stereomicroscope, sample even aperture distribution, pore size is about 140+20 μm, porosity 65%, after measured the powder of this example and consolidation liquid be in harmonious proportion after setting time be about 10 minutes, comprcssive strength is about 9.8MPa.
Fig. 4 is the comprcssive strength of the MPC bone cement adding different metal magnesium powder content in the present invention.As can be seen from the figure, the porous MPC bone cement that the method for the invention is prepared, its comprcssive strength presents the trend first reducing to increase afterwards along with the increase of content of magnesium.Its reason is due within the specific limits along with the increase of magnesium metal content added, and its pore-creating ability strengthens, and aperture and hole become large thus cause intensity to reduce.But after exceeding certain addition, due to the carrying out of magnesium accelerated reaction, setting time is shorter, in vigorous reaction process, produces tiny bubble have little time to overflow.The final small pore forming densification, so its intensity is far longer than the intensity of macropore bone cement.
Embodiment 8:
Take the magnesium oxide powder 3.9g (78%) of particle diameter 60 μm-70 μm, diammonium phosphate powder body 0.4g (8%), Ammonium biphosphate powder body 0.6g (12%), boric acid powder body 0.07g (1.4%), metal magnesium powder 0.03g (0.6%).By even for powder body grinding distribution in mortar in above-mentioned four, add 2.4ml normal saline, even walk is reconciled into dentistry modulation cutter, then 37 DEG C of 100% humidity environment solidification 2 hours is put into, by microscopic examination, sample even aperture distribution, pore size is about 450+20 μm, porosity 80%, comprcssive strength is about 4.8MPa.
Embodiment 9
Take the magnesium oxide powder 2.56g (51.2%) of particle diameter 60 μm-70 μm, ammonium phosphate powder body 2.3g (46%), boric acid powder body 0.125g (2.5%), metal magnesium powder 0.015g (0.3%).By even for powder body grinding distribution in mortar in above-mentioned four, add 0.75ml normal saline, even walk is reconciled into dentistry modulation cutter, then 37 DEG C of 100% humidity environment solidification 2 hours is put into, by microscopic examination, sample even aperture distribution, pore size is about 3504 ± 20 μm, porosity 80%, comprcssive strength is about 6.2MPa.
Embodiment 10
Take the magnesium oxide powder 2.75g (55%) of particle diameter 60 μm-70 μm, Ammonium biphosphate powder body 2.092g (41.85%), boric acid powder body 0.15g (3%), metal magnesium powder 0.008g (0.15%).By even for powder body grinding distribution in mortar in above-mentioned four, add 1ml normal saline, even walk is reconciled into dentistry modulation cutter, then 37 DEG C of 100% humidity environment solidification 2 hours is put into, by microscopic examination, sample even aperture distribution, pore size is about 450 ± 420 μm, porosity 75%, comprcssive strength is about 7.1MPa.
In order to better give prominence to superiority of the present invention, under identical experimental situation condition, prepare porous bone cement with the proportioning of embodiment, then by the porous bone cement prepared by the present invention and published patent (patent 1; CN101076344A; Patent 2:CN1162187C; Patent 3:CN102552986A) sample prepared of the method that provides carries out performance comparison, its result as shown in Table 1:
Properties of sample contrast table prepared by table 1 embodiment of the present invention and prior art
When preparing porous sample equally, no matter the sample prepared by the present invention all shows obvious advantage on pore-forming time, pore size and early anti pressured intension.
In the pore-forming time, compare patent 1 and patent 2 to need after implant into body in vivo slowly degraded thus form duct, spended time is longer, the pore-forming time of the present invention can be carried out artificial adjustment from 3 ~ 10 minutes as required and is namely completed poration process before implant into body, avoided pore-creating time and bone cell growth and crawl time unmatched problem.Compared to patent 3, although the pore-creating time of patent 3 is similar to the present invention, the present invention has a unexistent remarkable characteristic of patent 3 and the pore-creating time of the present invention can according to demand by regulating the addition of magnesium metal to regulate and control.
In pore size, compared to patent 1, patent 2, patent 3, no significant difference on pore size, but the effect of pore-forming, its pore size uniform, controllable of the porous material prepared by the present invention, can the content of magnesium metal be regulated according to specific needs realize regulation and control pore size object, this characteristic be other three patents incomparable.
In comprcssive strength, the porous sample prepared by the present invention, its comprcssive strength significantly will be better than patent 1 and patent 3, but its comprcssive strength is similar compared with patent 2, but the pore-forming time of patent 2 significantly will be weaker than the present invention.Its comprcssive strength of sample prepared by the present invention can regulate the content of magnesium metal according to specific needs to realize and regulate comprcssive strength object, this characteristic be other three patents incomparable (as shown in Figure 4).Combination property, advantage of the present invention wants much obvious compared with other three contrast patented technologies.
In sum, pore-creating mechanism of the present invention is different from the mechanism of patent 1 and patent 2, poration process and natural bone derived materials course synchronization carry out, when bone cement solidifies, pore-creating completes, after the implantation osteocyte can adhere to smoothly with hole in and normal growth, solve the problem that the cell growth time and the hole formation time that exist in patent 1 and patent 2 are difficult to mate.Contrast with patent 3, pore-creating of the present invention is the effect serving catalyst based on the metal magnesium powder added, and it promotes the formation of ammonia, achieves pore-creating; And the pore-creating in patent 3 reacts based on the metal magnesium powder added and subacid solution to produce hydrogen and realize pore-creating.
Compared with prior art, its pore-forming time of porous sample that the technology that the present invention adopts is prepared, comprcssive strength, pore size and porosity all can realize artificial adjustment by regulating the content of metal magnesium powder.This feature considerably increases the use approach of future products, and simple to operate.In addition the magnesium in bone cement can promote the growth of osteocyte to a certain extent thus accelerating wound healing after implant into body, alleviates the misery of patient.
The above embodiments are just in order to better explain the present invention, and it should not be construed limitation of the present invention.The technical scheme that those skilled in the art is formed according to equivalents of the present invention or equivalent replacement, all drops within rights protection scope of the present invention.
Claims (10)
1. a bone cement, is characterized in that, is made up of the component of following weight percentage:
Magnesium oxide 45-78wt%
Ammonium phosphate salt 20-50wt%
Retarder 0.5-10wt%
Magnesium powder 0.01-10wt%, and
Consolidation liquid, the liquid-solid ratio of described consolidation liquid and the mixture of above-mentioned material is 0.06-1.0ml/g.
2. bone cement according to claim 1, is characterized in that, described ammonium phosphate salt is one in Ammonium biphosphate, diammonium phosphate, ammonium phosphate or its mixture; Described retarder is boric acid or borate.
3. bone cement according to claim 1, is characterized in that, the granularity of described magnesium oxide, described ammonium phosphate salt, described retarder and described magnesium powder is 10 μm-80 μm.
4. bone cement according to claim 1, is characterized in that, the percentage by weight of described magnesium powder is between 0.01-0.6wt%.
5. bone cement according to claim 1, is characterized in that, described liquid-solid ratio is 0.1-0.25ml/g.
6. a preparation method for bone cement, comprises the following steps:
Step one gets all the raw material ready by following composition proportion (percentage by weight wt%):
Magnesium oxide 45-78%
Ammonium phosphate salt 20-50%
Retarder 0.5-10%
Magnesium powder 0.01-10wt%
The ratio of step 2 in 0.06-1.0ml/g in the mixture of said components adds consolidation liquid, mix homogeneously, pours natural molding in mould into.
7. the preparation method of bone cement according to claim 6, is characterized in that, described ammonium phosphate salt is one in Ammonium biphosphate, diammonium phosphate, ammonium phosphate or its mixture; Described retarder is boric acid or borate.
8. bone cement according to claim 6, is characterized in that, the granularity of described magnesium oxide, described ammonium phosphate salt, described retarder and described magnesium powder is 10 μm-80 μm.
9. bone cement according to claim 6, is characterized in that, the percentage by weight of described magnesium powder is between 0.01-0.6wt%.
10. bone cement according to claim 6, is characterized in that, the ratio adding described consolidation liquid is 0.1-0.25ml/g.
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| CN111888521B (en) * | 2020-06-11 | 2021-12-17 | 上海禾麦医学科技有限公司 | Bone repair material and preparation method thereof |
| CN112717206A (en) * | 2020-12-30 | 2021-04-30 | 杭州市萧山区第一人民医院 | Mesoporous calcium magnesium silicate/magnesium ammonium phosphate composite material and method for preparing bone cement and skeleton by using same |
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| CN101032632A (en) * | 2006-03-08 | 2007-09-12 | 中国科学院金属研究所 | Material for bone tissue engineering scaffold and making method thereof |
| CN102552986A (en) * | 2012-02-28 | 2012-07-11 | 河南科技大学 | Method for preparing porous bone cement by using metal porogen |
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| CN1307908A (en) * | 2001-02-22 | 2001-08-15 | 华东理工大学 | Inorganic bane adhesive and its application in body's hard tissue repair |
| CN101032632A (en) * | 2006-03-08 | 2007-09-12 | 中国科学院金属研究所 | Material for bone tissue engineering scaffold and making method thereof |
| CN102552986A (en) * | 2012-02-28 | 2012-07-11 | 河南科技大学 | Method for preparing porous bone cement by using metal porogen |
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