CN105000569B - Mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material, bone repair and its preparation method and application - Google Patents
Mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material, bone repair and its preparation method and application Download PDFInfo
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Abstract
The invention discloses mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material, bone repair and its preparation method and application.The preparation method of the mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material is：15wt%~20wt% mesoporous magnesium silicate, 10wt%~15wt% hydroxyapatite and 65wt%~75wt% polyether-ether-ketones are uniformly mixed, obtain mixed-powder；Then mixed-powder is mixed with absolute ethyl alcohol is entered, ultrasonic disperse, then evaporates absolute ethyl alcohol at 65 DEG C~80 DEG C, obtain composite powder；Using die pressing by the composite powder machine-shaping, both；The composite has good bioactivity and biocompatibility, has preferable mechanical compatibility with bone tissue, can stimulation of bone growth, accelerate knitting, reduce bone implant material after healing time.The bone repair has good biomechanics of bone compatibility and antibiotic property, and its intensity height, endurance, corrosion resistance are good, service life length.
Description
Technical field
The present invention relates to Material Field, more particularly to mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material and its
Preparation method and application, further relate to a kind of bone repair and preparation method thereof.
Background technology
The bone implant material of clinical practice at present is more titanium-based bone implant material and ceramic bone implant material, but these
The shortcomings that material all itself is difficult to overcome in the presence of some, for example, metal structure property differs greatly with bone, it is living to lack biology
Property, and bone information can not be easily caused with bon e formation Integrated implant, in addition, the dissolution of metal ion easily causes hydrops, inflammation and bad
Wait indefinitely phenomenon；For another example then there is the shortcomings of being not easy processing and forming, toughness is poor in ceramic bone implant material.Therefore, new replacement
The research and development of product are particularly important.
Polyether-ether-ketone (polyetheretherketone, PEEK) is a kind of excellent semi-crystalline thermoplastic's work of processing characteristics
Engineering plastics, PEEK modulus of elasticity and the modulus of elasticity of cortex bone approach, and have good biocompatibility, additionally have and put
The advantages that radiolucency, magnetic resonance imaging are without artifact.Therefore, PEEK is a kind of preferable orthopedic implanting material.
PEEK not only has excellent biocompatibility and biological stability, and fatigue resistance is good, corrosion resistance is strong；With
The modulus of elasticity of artificial bone of PEEK manufactures matches with bone tissue, and high intensity, hard wear resistant and mechanical through sterilizing repeatedly
Intensity is not degenerated.Oneself is designated as " optimal long-term bone grafting material " to PEEK, and obtains FDA (Food and Drug
Administration, food and medicine Surveillance Authority of the U.S.) certification, the U.S. develops the bone being chronically implanted with PEEK closes
Section, elbow joint etc..Therefore, PEEK has more obvious advantage than metal and ceramics, is implanted into suitable for internal long-term bone.But
PEEK lacks bioactivity, it is impossible to is combined with the firm key of people's bon e formation.
Hydroxyapatite (Ca10(PO4)6(OH)2, HA) and it is a kind of inorganic material, it is the main of inanimate matter in body bone tissue
Composition, substantial amounts of biocompatibility test prove hydroxyapatite it is nontoxic, it is non-stimulated, will not allergic reaction, not mutagenesis and not
Biological tissue is destroyed, therefore, hydroxyapatite has good biocompatibility, but its fragility is larger, poor mechanical property.
Magnesium silicate has good bioactivity, and compared with β-TCP, magnesium silicate has the skeletonization efficiency higher than β-TCP.Magnesium silicate is made pottery
Porcelain has good biodegradability, after being soaked in SBF, surface energy generation apatite layer.In addition, magnesium silicate is in physiologic ring
Can be discharged under border stimulates magnesium ion, the silicon ion of the propagation for promoting Gegenbaur's cell and differentiation.In grinding as biomaterial
In studying carefully, do not show have cytotoxicity to Gegenbaur's cell in testing in vitro, the material can lead in research in vivo
One calcium-phosphate layer of Surface Creation is crossed, so as to be combined closely with bone.However, magnesium silicate bioceramic is present, fragility is big, mechanical property
The shortcomings of not high and modulus of elasticity is insufficient, limit its application.
The content of the invention
The technical problems to be solved by the invention be the mechanical compatibility for overcoming existing bone renovating material it is bad and
Bone renovating material loosening and bone information caused by stress shielding are caused, or knitting speed is excessively slow, shortage bioactivity, and can not
The defects of with bon e formation secure bond.
The present invention provides a kind of mesoporous magnesium silicate and preparation method thereof, a kind of mesoporous magnesium silicate/hydroxyapatite/polyethers ether
Ketone composite and its preparation method and application, and one kind is by the mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite wood
Bone repair and preparation method thereof made from material.The uniform particle sizes of the mesoporous magnesium silicate, and mesoporous pore size is evenly distributed.This is mesoporous
Magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material has good bioactivity and biocompatibility, with bone tissue have compared with
Good mechanical compatibility, can stimulation of bone growth, accelerate knitting, reduce the healing time after bone implant material.The mesoporous silicon
Sour magnesium/hydroxyapatite/polyether-ether-ketone composite material it is simple for process, the mesoporous silicon can be accordingly adjusted according to clinical demand
The preparation technology of sour magnesium/hydroxyapatite/polyether-ether-ketone composite material repaiies to prepare the bone of different shape, specification and mechanical property
Complex.The bone repair has good biocompatibility, bioactivity, biomechanics of bone compatibility and antibiotic property, can shorten bone and be cured
The time is closed, its intensity height, endurance, corrosion resistance are good, service life length.After the bone repair implantation inflammation will not be caused anti-
Should, and the mechanical property such as its modulus of elasticity, toughness and fracture strength matches with people's bone photo, will not cause bone caused by stress shielding
The negative effect such as repair materials loosening and bone information, disclosure satisfy that the clinical needs for Bone Defect Repari.
The present invention solves above-mentioned technical problem by the following technical programs.
The invention provides a kind of preparation method of mesoporous magnesium silicate, it comprises the steps：
(1) P123, water and absolute ethyl alcohol are mixed, adds mixer stirring, until solution is clarified, at 35 DEG C~45 DEG C
Add hydrochloric acid to be stirred, then TEOS is added dropwise in solution dropwise, stirs to solution and white opacity occurs, then add six
Water magnesium nitrate, continue 2~3h of stirring, obtain reaction solution；Wherein, the mass ratio of P123, water and absolute ethyl alcohol is 1:(37~
37.5):1, P123 and the mass volume ratio of hydrochloric acid be 1g:(4~4.2) mL, P123 and TEOS mass ratio is 1:(2~2.5),
P123, the mass ratio of magnesium nitrate hexahydrate are 1:(1.4~1.6)；
(2) reaction solution is aged 48h at 95 DEG C~100 DEG C, filters and remove upper liquid, by sediment in 85 DEG C~90 DEG C
Under be dried, sinter 6-8h at 600 DEG C~650 DEG C, obtain mesoporous magnesium silicate.
In step (1), polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer that the P123 is known in the art
Thing (EO20PO70EO20)。
In step (1), the water is water commonly used in the art, generally deionized water.
In step (1), preferably 40 DEG C of the temperature for adding hydrochloric acid.
In step (1), the hydrochloric acid is hydrochloric acid commonly used in the art, the preferred 11.9mol/ of concentration of described hydrochloric acid
L。
In step (1), the TEOS is tetraethyl orthosilicate commonly used in the art.The speed of the dropwise addition preferably 30
Drop/min~50 drops/min.
In step (2), the method and condition of the ageing are this area conventional method and condition.The temperature of the ageing
It is preferred that 98 DEG C.The time preferred 48h of the ageing.The ageing is carried out typically in baking oven.
In step (2), the method and condition of the drying are this area conventional method and condition.The temperature of the drying
It is preferred that 85 DEG C.
In step (2), the method and condition of the sintering are this area conventional method and condition.The temperature of the sintering
It is preferred that 600 DEG C, the time preferred 7h of the sintering.
In the better embodiment of the present invention, the preparation method of the mesoporous magnesium silicate, it comprises the steps：
(1) 8.5g P123,240mL deionized water and 8g absolute ethyl alcohols are mixed, and stirs to solution and clarify, in 40
The hydrochloric acid that 20mL concentration is 11.9mol/L is added at DEG C to be stirred, and then 24g TEOS is added dropwise in solution, stirring is extremely
After white opacity occurs in solution, 29.5g magnesium nitrate hexahydrate is added, continues to stir 2.5h；
(2) reaction solution is aged 48h at 98 DEG C, then filters and remove upper liquid, sediment is done at 85 DEG C
It is dry, sinter 7h at 600 DEG C.
The mesoporous pore size of mesoporous magnesium silicate obtained by preparation method of the present invention is 2nm~5nm, and particle diameter is
0.5 μm~1 μm.
Present invention also offers a kind of preparation method of mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material, its
Comprise the steps：Raw material is uniformly mixed, obtains mixed-powder；Then absolute ethyl alcohol is poured into the mixed-powder, surpassed
Sound disperses, and then evaporates absolute ethyl alcohol at 65 DEG C~80 DEG C, obtains composite powder；The composite powder is added using die pressing
Work is molded；Wherein, the dosage of the mesoporous magnesium silicate accounts for 15wt%~20wt% of raw material gross weight, the dosage of hydroxyapatite
10wt%~15wt% of raw material gross weight is accounted for, the dosage of the polyether-ether-ketone accounts for 65wt%~75wt% of raw material gross weight；
The particle diameter of the polyether-ether-ketone is 10 μm~20 μm.
Wherein, preferably 10 μm~20 μm of the particle diameter of the polyether-ether-ketone.
Wherein, the method for the mixing and condition can be this area conventional method and condition, be defined by well mixed.Institute
Mixing is stated preferably to carry out in mixer.
Wherein, the dosage of the absolute ethyl alcohol is conventional amount used, is defined so that the mixed-powder is fully dispersed.The steaming
Send out preferably 75 DEG C of the temperature of absolute ethyl alcohol.Time preferred 30min~40min of the ultrasonic disperse.The work(of the ultrasonic disperse
Preferred 60W~the 90W of rate.
Wherein, the method for the die pressing and condition can be this area conventional method and condition.Described die pressing compared with
Carried out goodly by following operating methods：The mixed-powder is compressing, then heat up, sinter molding, you can；The heating
Speed is 1 DEG C/min~4 DEG C/min；The temperature of the sintering is 345 DEG C~370 DEG C；The soaking time of the sintering is
140min-180min, preferably 150min.
In the present invention, mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material for being obtained after the machine-shaping
Shape is unlimited.If the mould used in the machine-shaping is the mould of bone repair product, described mesoporous magnesium silicate/hydroxyl
Base apatite/polyether-ether-ketone composite material can be directly used as bone repair.If mould used is not bone in the machine-shaping
The mould of dummy product, then it can be operated by follow-up working process, such as the process such as grinding, machining, to prepare
Need the bone repair of shape.
Present invention also offers a kind of mesoporous magnesium silicate/hydroxyapatite/polyethers ether as obtained by above-mentioned preparation method
Ketone composite.
In the present invention, described mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material is to be a kind of with mesoporous silicic acid
The composite of magnesium/hydroxyapatite reinforced polyether ether ketone.
Present invention also offers the mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material in bone repair
Application.
Wherein, described bone repair is backbone bone repair or tooth implant.Described backbone bone repair is also referred to as
Invasive lumbar fusion device, including strength Invasive lumbar fusion device and chest/waist Invasive lumbar fusion device.
Present invention also offers a kind of preparation method of bone repair, it comprises the steps：By mesoporous magnesium silicate, hydroxyl
Apatite and polyether-ether-ketone uniformly mix, and obtain mixed powder；Then the mixed-powder is mixed with absolute ethyl alcohol, ultrasound point
Dissipate, then evaporate absolute ethyl alcohol at 65 DEG C~80 DEG C, obtain composite powder；The composite powder is poured into bone repair product
Mould in, molding sintering shaping；The dosage of the mesoporous magnesium silicate accounts for 15wt%~20wt% of raw material gross weight, hydroxyl phosphorus
The dosage of lime stone accounts for 10wt%~15wt% of raw material gross weight, and the dosage of the polyether-ether-ketone accounts for the 65wt% of raw material gross weight
~75wt%；The particle diameter of the polyether-ether-ketone is 10 μm~20 μm.
Wherein, preferably 10 μm~20 μm of the particle diameter of the polyether-ether-ketone.
Wherein, the method for the mixing and condition can be this area conventional method and condition, be defined by well mixed.Institute
Mixing is stated preferably to carry out in mixer.
Wherein, the dosage of the absolute ethyl alcohol is conventional amount used, is defined so that the mixed-powder is fully dispersed.The steaming
Send out preferably 75 DEG C of the temperature of absolute ethyl alcohol.Time preferred 30min~40min of the ultrasonic disperse.The work(of the ultrasonic disperse
Preferred 60W~the 90W of rate.
Wherein, the mould of the bone repair product is to prepare conventional use of mould, preferably ridge during bone repair product
The mould of spinous process of the seventh cervical vertebra dummy or the mould of tooth implant.Described backbone bone repair is also referred to as Invasive lumbar fusion device, including neck/vertebra
Between fusion device and chest/waist Invasive lumbar fusion device.
Wherein, the method for the molding sintering shaping and condition can be this area conventional method and condition.Described mould
Sinter molding is pressed preferably to be carried out by following operating methods：Described mixed-powder is compressing, then heat up, sinter molding,
；The speed of the heating is 1 DEG C/min；The temperature of the sintering is 345 DEG C~370 DEG C；The soaking time of the sintering
For 140min-180min, preferably 150min.
Present invention also offers one kind bone repair as made from above-mentioned preparation method.
Wherein, described bone repair is backbone bone repair or tooth implant.Described backbone bone repair is also referred to as
Invasive lumbar fusion device, including strength Invasive lumbar fusion device and chest/waist Invasive lumbar fusion device.
In the present invention, the shape and specification of the bone repair can be according to being actually needed by selecting different moulds to carry out
Change.
In the present invention, the mechanical performance index of the Bone Defect Repari approximately as：
Modulus of elasticity is 4.5GPa~6GPa, and compression strength is 100MPa~170GPa, tensile strength be 70MPa~
110MPa, bending strength are 85MPa~130MPa.
It on the basis of common sense in the field is met, above-mentioned each optimum condition, can be combined, it is each preferably real to produce the present invention
Example.
Agents useful for same and raw material of the present invention are commercially available.
The positive effect of the present invention is：
(1) particle diameter of mesoporous magnesium silicate of the invention is 0.5 μm~1 μm, and its particle diameter distribution is uniform, and its mesoporous pore size is
2nm~5nm, and mesoporous pore size is evenly distributed.
(2) mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material of the invention is simple for process, can root
The preparation technology of the mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material is accordingly adjusted according to clinical demand to prepare not
The bone repair of similar shape, specification and mechanical property.
(3) mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material of the invention have good bioactivity and
Biocompatibility, have preferable mechanical compatibility with bone tissue, can stimulation of bone growth, accelerate knitting, reduce bone implantation material
Healing time after material.
(4) bone repair of the invention has good biocompatibility, bioactivity, biomechanics of bone compatibility, can shorten
Bone healing time.It will not cause inflammatory reaction, and its modulus of elasticity, toughness and fracture strength etc. after being implanted into using the bone repair
Mechanical property matches with people's bone photo, will not cause the negative effect such as bone renovating material loosening and bone information caused by stress shielding,
It disclosure satisfy that the clinical needs for Bone Defect Repari.
Brief description of the drawings
In order to illustrate more clearly of technical scheme, letter will be made to the required accompanying drawing used in embodiment below
Singly introduce, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for the common skill in this area
For art personnel, on the premise of not paying creative work, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is the stereoscan photograph and transmission electron microscope photo of the mesoporous magnesium silicate in embodiment 1.
Fig. 2 is the mesoporous magnesium silicate/hydroxyapatite/polyethers used in the cytotoxicity test experiment of effect example 2
The shape picture of ether ketone composite sample (12 × 2mm of Ф).
Fig. 3 is that mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone of progress cytotoxicity experiment in effect example 2 is multiple
Condensation material optical density figure.
Fig. 4 is mesoporous magnesium silicate/hydroxyapatite/polyethers ether that the cell adherence proliferation experiment of effect example 3 measures
The comparison diagram of the relative proliferation rate of ketone composite and the relative proliferation rate of polyetheretherketonematerials materials.
Fig. 5 is that the cell adherence of effect example 3 breeds stereoscan photograph.
Fig. 6 is the sample photo of the bone repair in effect example 4.
Fig. 7 is to be implanted into the gross examination of skeletal muscle photo after Bone Defect Repari March in effect example 4 at the dog femoral defect.
Fig. 8 is implanted into the histotomy at dog femoral defect after 3 months for the bone repair in effect example 4.
Fig. 9 is to be implanted into the gross examination of skeletal muscle photo after Bone Defect Repari March in effect example 4 at the dog Alveolar Bone Defect.
Figure 10 is implanted into the histotomy at dog Alveolar Bone Defect after 3 months for the bone repair in effect example 4.
Embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described reality
Apply among a scope.The experimental method of unreceipted actual conditions in the following example, conventionally and condition, or according to business
Product specification selects.
In following embodiments, P123 used relative molecular mass is 5800, is purchased from Aldrich.
Embodiment 1
A kind of preparation method of mesoporous magnesium silicate, it comprises the steps：
(1) 8.5g P123,240mL deionized water and 8g absolute ethyl alcohols are mixed, and stirred to solution clarification, in
The hydrochloric acid that 20mL concentration is 11.9mol/L is added at 40 DEG C to be stirred, and then 24g TEOS is added dropwise in solution, stirred
After there is white opacity to solution, 29.5g magnesium nitrate hexahydrate is added, continues to stir 2.5h, obtains reaction solution；
(2) reaction solution is aged 48h at 98 DEG C, then filters and remove upper liquid, sediment is done at 85 DEG C
It is dry, 7h is sintered at 600 DEG C, obtains mesoporous magnesium silicate.
The stereoscan photograph and transmission electron microscope photo of the mesoporous magnesium silicate/hydroxyapatite see respectively Fig. 1 (a), (b) and
Fig. 1 (c), (d)；The mesoporous pore size of the mesoporous magnesium silicate/hydroxyapatite is in 2nm~5nm, and particle diameter is 0.5~1 μm, its particle diameter
It is evenly distributed.
Embodiment 2
The preparation method of mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material, it comprises the steps：
By 1.5kg (15wt%) hydroxyapatite, 6.5kg (65wt%) polyether-ether-ketone (particle diameter is 10 μm) and 2kg
Mesoporous magnesium silicate made from (20wt%) embodiment 1 uniformly mixes in mixer, obtains mixed-powder；By mixed-powder with it is anhydrous
Ethanol mixes, and disperses 30min with 60W power ultrasonic, is subsequently placed in evaporation absolute ethyl alcohol in 65 DEG C of baking ovens；Then will with mould
Composite powder is compressing (using the mould of non-bone repair product), then is heated up in sintering furnace, sinter molding, both；Its
In, sintering temperature is 350 DEG C；The programming rate of sintering furnace is 1 DEG C/min；Soaking time is 140min.Mesoporous magnesium silicate/the hydroxyl
The mechanical property of base apatite/polyether-ether-ketone composite material is shown in Table 1.
Embodiment 3
The preparation method of bone repair, it comprises the following steps：
By 1.5kg (15wt%) hydroxyapatite powder, 7kg (70wt%) polyether-ether-ketone (particle diameter be 15 μm) and
Uniformly mixed 1.5kg mesoporous magnesium silicate made from (15wt%) embodiment 1 carries out raw material in mixer, obtain mixed-powder；Will
Mixed-powder mixes with absolute ethyl alcohol, disperses 30min with 70W power ultrasonic, is subsequently placed in the anhydrous second of evaporation in 70 DEG C of baking ovens
Alcohol, obtain composite powder；Then it is with mould that composite powder is compressing (mould of bone repair product), then risen in sintering furnace
Temperature, sinter molding, both；Wherein, sintering temperature is 360 DEG C；The programming rate of sintering furnace is 1 DEG C/min；Soaking time is
140min.The mechanical property of the bone repair is shown in Table 1.
Embodiment 4
The preparation method of mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material, it comprises the following steps：
By 1kg (10wt%) hydroxyapatite, 7kg (70wt%) polyether-ether-ketone (particle diameter is 15 μm) and 2kg
Mesoporous magnesium silicate made from (20wt%) embodiment 1 uniformly mixes in mixer, obtains mixed-powder；By mixed-powder with it is anhydrous
Ethanol mixes, and disperses 40min with 60W power ultrasonic, is subsequently placed in evaporation absolute ethyl alcohol in 80 DEG C of baking ovens；Then will with mould
Composite powder is compressing (using the mould of non-bone repair product), then is heated up in sintering furnace, sinter molding, both；Its
In, sintering temperature is 370 DEG C；The programming rate of sintering furnace is 1 DEG C/min；Soaking time is 170min.Mesoporous magnesium silicate/the hydroxyl
The mechanical property of base apatite/polyether-ether-ketone composite material is shown in Table 1.
Embodiment 5
The preparation method of mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material, it comprises the steps：
By 1kg (10wt%) hydroxyapatite, 7.5kg (75wt%) polyether-ether-ketone (particle diameter is 10 μm) and 1.5kg
Mesoporous magnesium silicate made from (15wt%) embodiment 1 carries out raw material in mixer and uniformly mixed, and obtains mixed-powder；By mixed powder
End mixes with absolute ethyl alcohol, disperses 35min with 70W power ultrasonic, is subsequently placed in evaporation absolute ethyl alcohol in 75 DEG C of baking ovens, must answer
Close powder；Then it is with mould that composite powder is compressing (using the mould of non-bone repair product), then risen in sintering furnace
Temperature, sinter molding, produce；Wherein, sintering temperature is 365 DEG C；The programming rate of sintering furnace is 2 DEG C/min；Soaking time is
180min.The mechanical property of the mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material is shown in Table 1.
Embodiment 6
The preparation method of mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material, it comprises the steps：
By 1.5kg (15wt%) hydroxyapatite, 6.5kg (65wt%) polyether-ether-ketone (particle diameter is 10 μm) and 2kg
Mesoporous magnesium silicate made from (20wt%) embodiment 1 carries out raw material in mixer and uniformly mixed, and obtains mixed-powder；By mixed powder
End mixes with absolute ethyl alcohol, disperses 30min with 90W power ultrasonic, is subsequently placed in evaporation absolute ethyl alcohol in 70 DEG C of baking ovens, must answer
Close powder；Then it is with mould that composite powder is compressing (using the mould of non-bone repair product), then risen in sintering furnace
Temperature, sinter molding, produce；Wherein, sintering temperature is 355 DEG C；The programming rate of sintering furnace is 2 DEG C/min；Soaking time is
150min.The mechanical property of the mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material is shown in Table 1.
Comparative example 1
Raw material：1kg hydroxyapatite, 8kg polyether-ether-ketones (particle diameter is 10 μm) and mesoporous silicon made from 1kg embodiments 1
Sour magnesium, the preparation of composite is carried out according to the preparation method of embodiment 2.The mechanical property of the composite is shown in Table 1.
Comparative example 2
Raw material：2kg mesoporous magnesium silicate, 1kg hydroxyapatite and 7kg polyether-ether-ketones (particle diameter is 10 μm), according to reality
The preparation method for applying example 2 carries out the preparation of composite.The mechanical property of the composite is shown in Table 1.
Comparative example 3
Raw material：1kg hydroxyapatite, 4kg polyether-ether-ketones (particle diameter is 10 μm) and mesoporous silicon made from 5kg embodiments 1
Sour magnesium, the preparation of composite is carried out according to the preparation method of embodiment 2.The mechanical property of the composite is shown in Table 1.
Effect example 1
Mechanical property test：
Mechanics Performance Testing, test result are carried out to the bone repair of embodiment 2~6 and comparative example 1~3 to be shown in Table
1。
The mechanical property of the bone repair of 1 each embodiment of table and comparative example
From table 1, compared to the composite obtained by comparative example, the mesoporous magnesium silicate/hydroxy-apatite of the present invention
The modulus of elasticity of stone/polyether-ether-ketone composite material and people's bone is closer, and the parameters index in mechanical property is more excellent, very
It is adapted as the alternative materials (bone and tooth) of human body hard tissue.
Effect example 2
The cytotoxicity experiment of mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material：
Cytotoxicity is carried out to mesoporous magnesium silicate/hydroxyapatite made from embodiment 2 and 5/polyether-ether-ketone composite material
Experiment, wherein sample diameter is 10mm, thickness 2mm, is specifically shown in Fig. 2.The specific method of cytotoxicity experiment is as follows：
According to ISO：The biological safety of 10993-5 cytotoxicity standard testing composites.At 37 DEG C, two kinds of samples
(200mg/mL) soaks 24h in serum-free cell culture medium, filters to obtain leaching liquor.Will be into fiber with the concentration in 3 × 102/ holes
Cell is inoculated into 96 hole tissue culturing plates, continues after being incubated 1 day, discards culture medium, PBS 3 times；Add containing 10%FBS's
Leaching liquor, continue culture 1 day；Material leaching liquor not plus containing 10%FBS is as experiment blank control group.In testing time point
When, 30 microlitres of MTT solution are added per hole, are continued after being incubated culture 4h, nutrient solution is discarded, PBS 3 times, it is micro- that 100 is added per hole
DMSO is risen, after being stored at room temperature 10 minutes, with ELIASA at 490nm wavelength, the absorbance of solution is surveyed, sees Fig. 3.Can by Fig. 3
See, compared with blank control (tissue culturing plate TCP), the absorbance of experimental group (sample of embodiment 1 and 4) does not have conspicuousness
Difference, show that both composites have no adverse effect to fibroblastic growth.It is computed understanding, in material leaching liquor
Cell and blank control group cell survival rate ratio all more than 95%, it was demonstrated that the two samples are equal to fibroblast
There is no toxicity.
Effect example 3
Cell adherence proliferation experiment
Cell adherence is carried out to mesoporous magnesium silicate/hydroxyapatite made from embodiment 2 and 5/polyether-ether-ketone composite material
Proliferation experiment, wherein sample diameter are 10mm, thickness 2mm, are specifically shown in Fig. 2.The specific method of cell adherence proliferation experiment is such as
Under：
(1) cell proliferation experiment is carried out using mtt assay, by two kinds of samples (every kind of three groups of Duplicate Samples, polyetheretherketonematerials materials)
With the culture that MC3T3-E1 is carried out containing 10% hyclone nutrient solution, it is inoculated with every hole 1W cells, respectively at 1,3,5 day, per hole
Add the μ L of MTT solution 40, continue to cultivate 4h, terminate culture, it is careful to draw culture supernatant in hole, add 150 μ L DMSO per hole, take off
Color shaking table shakes 10min, crystal is selected 490nm (570nm) wavelength after fully dissolving, is determined on enzyme-linked immunosorbent assay instrument
Each hole absorbance value, obtains result, as a result such as Fig. 4.
(2) MC3T3-E1 cells are seeded in two kinds of samples (three groups of Duplicate Samples, polyetheretherketonematerials materials) with every hole 1w quantity
Cultivated, respectively at observing cell adherence situation after 12h, 24h are fixed cell using fixer under ESEM, such as schemed
5.(1) and (3) is cell adherence situation in polyether-ether-ketone group in Fig. 5, and (2), (4) are mesoporous magnesium silicate/hydroxyapatite/polyethers
Ether ketone composite group cell adherence situation, the results showed that, two kinds of material surfaces have cell adherence and propagation, but mesoporous silicic acid
The cell quantity of magnesium/hydroxyapatite/polyether-ether-ketone composite material group adhesion is more and with preferably adhesion form, shows it
With more preferable bioactivity and cell compatibility.
Effect example 4
Animal implantation experiment：
(1) by bone repair (concrete shape is shown in Fig. 6) the implantation dog femoral defect of 8 made dog femoral of embodiment.Fig. 7 is
The gross examination of skeletal muscle photo that digital camera is taken the photograph after being implanted into 3 months, signified arrow is implantation bone repair.Fig. 8 is to repair this bone
Histotomy at complex implantation dog femoral defect after 3 months.In Fig. 8, B represents bone parts, and M represents material part, arrow
Meaning is material and the bound fraction of bone.Fig. 8 is visible, and made bone repair is with bone directly in conjunction with junction is without connective tissue (bone
Integrate), therefore this dummy has good biocompatibility and bioactivity, can be used as body implanting material, repairs or substitute people
Body tissue.As a result show, the bone repair can promote bone tissue to grow, and firmly knot is directly formed with its bone tissue
Close.
(2) the made bone repair (outward appearance is shown in Fig. 6) of embodiment 8 is implanted at Labrador Retriever Alveolar Bone Defect, raising three
Taken out after month, outward appearance photo is shown in Fig. 9, and arrow meaning is former defect position.Picture is visible, and material and tissue at dog defect are tight
Close combination, and do not occur inflammation and other adverse reactions, complete Alveolar Bone Defect reparation.By its gained picture of cutting into slices for figure
The representative part of 10, wherein B be bone tissue part, and M represents material part, arrow it is signified for both boundary lines, by Tu Ke get, with reference to
Directly combined closely (Integrated implant) with bone tissue without connective tissue, material at place.Thus illustrate, dummy promotes its bone tissue
Growth, bone repair is stable with bone tissue and combines closely, and is connected as an entirety, completes the replacement reparation of Cranial defect.
Described above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (7)
1. a kind of preparation method of mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material, it is characterised in that it includes
Following steps：
Raw material is uniformly mixed, obtains mixed-powder, the raw material is mesoporous magnesium silicate, hydroxyapatite and polyether-ether-ketone, institute
The mesoporous pore size for giving an account of hole magnesium silicate is 2nm~5nm, and the particle diameter of the mesoporous magnesium silicate is 0.5 μm~1 μm；Then described
Absolute ethyl alcohol is poured into mixed-powder, ultrasonic disperse, then absolute ethyl alcohol is evaporated at 65 DEG C~80 DEG C, obtains composite powder；
Using die pressing by the composite powder machine-shaping, produce；Wherein, the dosage of the mesoporous magnesium silicate accounts for raw material gross weight
15wt%~20wt%, the dosage of hydroxyapatite account for 10wt%~15wt% of raw material gross weight, the use of the polyether-ether-ketone
Amount accounts for 65wt%~75wt% of raw material gross weight；The particle diameter of the polyether-ether-ketone is 10 μm~20 μm.
2. preparation method as claimed in claim 1, it is characterised in that the particle diameter of the polyether-ether-ketone is 10 μm~20 μm；With/
Or, the temperature of the evaporation absolute ethyl alcohol is 75 DEG C；It is described super and/or the time of the ultrasonic disperse is 30min~40min
The scattered power of sound is 60W~90W；And/or the die pressing is carried out according to following operating method：By the mixed-powder pressure
Type is made, then heats up, sinter molding, you can；The speed of the heating is 1 DEG C/min~4 DEG C/min；The temperature of the sintering is
345 DEG C~370 DEG C；The soaking time of the sintering is 140min~180min.
A kind of 3. mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone obtained by preparation method as described in claim 1 or 2
Composite.
4. a kind of mesoporous magnesium silicate/hydroxyapatite/polyether-ether-ketone composite material as claimed in claim 3 is in bone repair
Application.
5. a kind of preparation method of bone repair, it is characterised in that it comprises the following steps：Raw material is uniformly mixed, mixed
Powder is closed, the raw material is mesoporous magnesium silicate, hydroxyapatite and polyether-ether-ketone；Then by the mixed-powder and absolute ethyl alcohol
Mixing, ultrasonic disperse, then evaporates absolute ethyl alcohol at 65 DEG C~80 DEG C, obtains composite powder；The composite powder is poured into
In the mould of bone repair product, molding sintering shaping；The dosage of the mesoporous magnesium silicate account for the 15wt% of raw material gross weight~
20wt%, the dosage of hydroxyapatite account for 10wt%~15wt% of raw material gross weight, and the dosage of the polyether-ether-ketone accounts for raw material
65wt%~75wt% of gross weight；The particle diameter of the polyether-ether-ketone is 10 μm~20 μm.
6. preparation method as claimed in claim 5, it is characterised in that the particle diameter of the polyether-ether-ketone is 10 μm~20 μm；With/
Or, the temperature of the evaporation absolute ethyl alcohol is 75 DEG C；It is described super and/or the time of the ultrasonic disperse is 30min~40min
The scattered power of sound is 60W~90W；And/or the mould or tooth that the mould of the bone repair product is backbone bone repair
The mould of planting body；And/or the molding sintering shaping is carried out according to following operating method：The mixed-powder is pressed into
Type, then heat up, sinter molding；The speed of the heating is 1 DEG C/min；The temperature of the sintering is 345 DEG C~370 DEG C；It is described
The soaking time of sintering is 140min~180min.
A kind of 7. bone repair as made from the preparation method of claim 5 or 6.
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| CN114366851B (en) * | 2021-12-31 | 2022-09-02 | 江苏阳生生物股份有限公司 | Bone repair material for massive defects of mandible |
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| CN104649284A (en) * | 2015-02-05 | 2015-05-27 | 华东理工大学 | Mesoporous magnesium silicate-calcium sulfate hemihydrate composite material, and preparation method and application thereof |
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