CN107837419A - A kind of porous hydroxyapatite - Google Patents

A kind of porous hydroxyapatite Download PDF

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Publication number
CN107837419A
CN107837419A CN201610834316.XA CN201610834316A CN107837419A CN 107837419 A CN107837419 A CN 107837419A CN 201610834316 A CN201610834316 A CN 201610834316A CN 107837419 A CN107837419 A CN 107837419A
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porous hydroxyapatite
hydroxyapatite
vestibule
bone
porous
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CN201610834316.XA
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叶雷
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Chongqing Runze Pharmaceutical Co Ltd
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Chongqing Runze Pharmaceutical Co Ltd
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Priority to CN201610834316.XA priority Critical patent/CN107837419A/en
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/12Phosphorus-containing materials, e.g. apatite
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/42Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
    • A61L27/425Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of phosphorus containing material, e.g. apatite
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56Porous materials, e.g. foams or sponges
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention discloses a kind of medical porous hydroxyapatite, the material body of the porous hydroxyapatite is formed by vestibule and around the cavity wall of vestibule, vestibule is insertion, and the unit volume of the porous hydroxyapatite absorbs energy and is not less than 1.08 × 10 at the end of the plateau stress stage‑5J/mm3, this kind of medical porous hydroxyapatite have good energy absorption capability, can meet the needs of body bone tissue is grown into, and the spongiosa Bone Defect Repari implant small for bearing load, osteanagenesis effect is good after implantation.

Description

A kind of porous hydroxyapatite
Technical field
The present invention relates to porous material, more particularly to a kind of porous hydroxyapatite for medical embedded material.
Background technology
As the number of patients with all kinds of clinical orthopaedicses diseases and wound is increasing, people are to osseous tissue renovating material Demand increasingly increase.Hydroxyapatite is similar to the inanimate matter composition and crystal structure of skeleton, has excellent biology living Property and biocompatibility, it is considered to be one of current bioactive ceramics most representative, research is the most active, can conduct Human body bone renovating material and bone tissue engineering stent material, it is widely used in the clinical fields such as orthopaedics, dentistry and the reparation of cranium face.It is more Hole hydroxylapatite ceramic, in addition to general bioactive ceramics advantage, due to itself having loose structure, therefore it is more suitable Together in defect of human body bone reparation.The connectivity pore structure of both macro and micro can existing for inside Porous Hydroxyapatite Ceramic Growing into for bone tissue is promoted to intersect combination between bone tissue, so as to form more firm implant-bone interface.Secondly, it is more Hole hydroxylapatite ceramic pore structure can be not only body fluid microcirculation, oxygen and nutriment supply and metabolite discharge Good microenvironment is provided, is alternatively arranged as loading, discharging the excellent carrier of gene and medicine.In addition, Porous Hydroxyapatite Ceramic It can also be rebuild in bone tissue and serve as bone tissue engineering stent material in regenerative process.Therefore, Porous Hydroxyapatite Ceramic is made For a kind of function admirable Bone Defect Repari and bone tissue engineering stent material, countries in the world research is caused in field of biomedical materials Person's extensive concern.
People have carried out many researchs to porous hydroxyapatite, as Duan Xiang et al. is more in order using colloid crystal templating preparation Hole hydroxyapatite, and the performance of material is characterized by the means of testing such as X diffraction analysis, field emission scanning electron microscope analysis (Section is auspicious etc., the preparation of ordered porous hydroxyapatite and performance characterization, Shanghai City biomaterial for medical purpose seminar in 2007);Meter Chen Hong carried out porous hydroxyapatite bioactivity and Study on biocompatibility (meter Chen Hong, porous light base apatite HA's Electrochemistry formated and formation mechenism, Shanghai Normal University, 2011);Wang Lili etc. has carried out gel forming method and has prepared porous light base Apatite technique study, and with the in-vitro simulated biocompatibility that have studied light base apatite, it have studied intensity and porosity Relation(Wang Lili etc., gel forming method prepare porous light base apatite bioceramic and its performance study, Materials Science and Engineering Journal Feb.2006);But medical embedded material made from this series of studies achievement, practical application effect are bad all the time. At present, either document report or porous hydroxyapatite medical embedded material seen by the market, be implanted into human body after, people Body bone tissue can not be normally grown into implantation material, i.e., this implantation material can not realize bone tissue regeneration, it is impossible to as real Bone renovating material in meaning.
The content of the invention:
It is an object of the invention to provide a kind of good medical embedded regrown material of bone growth, Bone Defect Repari effect-more of being advantageous to Hole hydroxyapatite material.
It has been recognised by the inventors that being implanted into regrown material as bone, it needs that there is certain impact resistance to avoid structure Collapse, it is often more important that energy absorption possessed by it will be more beneficial for the growing into meet that bone renovating material should have of bone tissue The real regeneration function having.
The object of the invention is achieved through the following technical solutions:
A kind of porous hydroxyapatite, the material body of the porous hydroxyapatite are formed by vestibule and around the cavity wall of vestibule, Vestibule is insertion, it is characterised in that:The porosity of the porous hydroxyapatite is not more than 90%, and unit volume absorbs energy It is not less than 1.08 × 10 at the end of the plateau stress stage-5 J/ mm3.Such porous hydroxyapatite as bone implantation piece, Bone tissue is particularly conducive to start to grow.After the implantation, because it has more appropriate energy absorption capability, there is appropriate delay Effect is rushed, the good growing environment that bone tissue can be supplied to just to grow into after implantation, is advantageous to bone tissue regeneration, this porous hydroxyapatite Apatite is applied to the small spongiosa Bone Defect Repari implant of stress.
Furtherly, described porous hydroxyapatite, its aperture are 200 μm -500 μm, and this kind of aperture is advantageous to bone tissue length Enter.
Furtherly, the ratio of described porous hydroxyapatite, its percent opening and porosity is more than 96%, be ensure that porous Hydroxyapatite hole is inside and outside insertion, is advantageous to moving tissue liquid, and bone tissue is grown into.
Furtherly, described porous hydroxyapatite is the composite using hydroxyapatite as base material.
Furtherly, above-mentioned composite be porous hydroxyapatite and zirconium dioxide, carbon fiber, biological glass fiber, Macromolecular fibre, polylactic-co-glycolic acid, polyether-ether-ketone, polyamide, ultra-high molecular weight polyethylene, PLA or graphene Composite.Composite can increase its obdurability, energy absorption, can promote adhesion, the differentiation of cell again.
Beneficial effects of the present invention:
Porous hydroxyapatite provided by the invention, due to having done preferable selection to its energy absorption capability, it not only has Appropriate buffering effect, impact resistance, it is often more important that its first growth to bone tissue, the growth for growing into effect and bone tissue Speed is helpful.It can meet the small spongiosa Bone Defect Repari implant bone group of the needs of body bone tissue is grown into, particularly stress The demand grown into is knitted, the osteanagenesis after implantation works well, and is a kind of ideal bone renovating material.
Porous hydroxyapatite provided by the invention is implanted into material, is mutually communicated between its vestibule, vestibule and external environment It is insertion, the porous hydroxyapatite of this structure is particularly conducive to the transmission of tissue fluid, and bone tissue is grown into, as implantation Body is firmly combined with body bone tissue, good biocompatibility, function admirable, is a kind of bone-regeneration material of real meaning.
Because body bone tissue is often in motion, power can be also often subject to after being implanted into human body as bone implant material Effect.And porous hydroxyapatite implantation material provided by the invention, there is suitable energy absorption capability, not only have good Buffering effect, stronger impact resistance, external force can be avoided to cause implant and bone tissue to damage and structural collapse, maintained just Normal physiological function;And these active forces can be transferred to body bone tissue by it, bone cell growth is stimulated so that bone tissue can be grown Enter to implant, and upgrowth situation is good, realizes osteanagenesis.
Embodiment
The embodiment of the present invention will be explained below, embodiment is given premised on technical solution of the present invention Detailed embodiment and specific operating process are gone out, but protection scope of the present invention is not limited only to embodiment disclosed below.
Embodiments of the invention are given in detail below.
Embodiment 1:
The porous hydroxyapatite of the present embodiment, it is mutually communicated between its vestibule and vestibule, vestibule, should with extraneous and insertion The aperture of the vestibule of porous hydroxyapatite is 300 μm -500 μm, and porosity 90%, preparation method is as follows:
(1)Take particle diameter 40nm-80nm hydroxylapatite powder, PVAC polyvinylalcohol -1750, polyethylene glycol PEG-800, distilled water, By it according to hydroxylapatite powder:PVAC polyvinylalcohol -1750:Polyethylene glycol PEG-800:It is 45 to distill water weight ratio:6:3:46 Proportional arrangement, first 3% polyethylene glycol PEG-800 is mixed with 39% distilled water, is then gradually added into hydroxylapatite powder 45%, while stirred with constant temperature blender with magnetic force, until there is no bubble;By 6% PVAC polyvinylalcohol -1750 and 7% distilled water Mixing, is heated to 90 DEG C with ultrasonic cleaner, then adds above-mentioned hydroxylapatite powder slurry, continues stirring 1 hour, then use Ultrasonic disperse 30min.
(2)Take the polyurethane foam that aperture is 450 μm -650 μm, the 0226g/cm of density 0.3, cleaned, dried with acetone Hydroxylapatite powder slurry is immersed afterwards, and equably unnecessary slurry is extruded with pinch roller, 24h is dried at room temperature, is put into drying In 60 DEG C of dry 12h in case.
(3)Base substrate after polyurethane foam is impregnated is put into microwave vacuum agglomerating plant, sets voltage 220V, frequency 2.45GHz, heated up with 6 DEG C/min speed, be heated to being incubated 1h at 540 DEG C, be then warming up to 12 DEG C/min speed 1200 DEG C, 1.5 hours are incubated, furnace cooling, that is, porous hydroxyapatite is made.
The porosity of the present invention refers to that material internal pore volume accounts for the percentage of its cumulative volume.Porosity is according to direct body Product weight method measures, and first measures the quality of sample, then measures the volume of sample, according to the volume of sample and sample material dense body Density draws the quality of the dense body suitable with the volume of sample, and the difference of the quality and sample mass is again divided by the volume with sample The quality of suitable dense body, then it is multiplied by 100% porosity for being sample.Measure obtained porous hydroxyapatite hole Gap rate is 90%.
The aperture of above-mentioned porous hydroxyapatite finished product is measured by GB/T5249-1985, measuring aperture is 300μm-500μm。
Test percent opening according to GB/T5163-2006, according to the standard, after sample complete wetting the volume of contained oil divided by The volume of sample multiplied by with 100% be material percent opening, calculated after test further according to porosity, draw percent opening with The ratio of porosity is 98.7%.Illustrate inside vestibule and be to penetrate with external world.
Experiment is compressed with the testing machines of Instron 8801 according to GB/T 1964-1996, sample takes Φ 4mm × 6mm, 26 DEG C of test temperature, unit volume absorbs energy value for 1.1 × 10 at the end of measuring the plateau stress stage-5 J/mm3, the present invention Described unit volume is absorbed at the end of energy refers in porous material compressive stress strain curve from zero to the plateau stress stage Domain integral obtained by energy value.
Above-mentioned porous hydroxyapatite is made to the particle of Φ 4 × 6mm sizes, packs, treats after gamma-radiation sterilizes With.
Choose stone age ripe new zealand white rabbit 2, male and female with 3% yellow Jackets in intraperitoneal injection of anesthesia regardless of being moved Thing, after general anesthesia, hair at pygostyle is rejected, cuts pygostyle outer skin, hypodermis, muscle, periosteum is peeled off, with dentistry dental drill Drill on pygostyle, respectively fill in above-mentioned porous hydroxyapatite particles, a rabbit plug one, then layering suture.Art Finish intramuscular injection penicillin Incision infection prevention.12 weeks after operation, 24 weeks each tail bones put to death 1, remove implantation porous hydroxyapatite Bone, the soft tissue on surface is removed as far as possible.Implantation material is taken out into observation, porous hydroxyapatite does not split for 12 weeks, 24 weeks Line, it is damaged the defects of, test material is fixed, embed, cut into slices, piece is thick 4 μm, and Goldner's trichrome stainings observe porous material The internal area of new bone situation of material.
Observation indicate that porous hydroxyapatite 12 weeks after operation bone tissue grows into the 4% of implant pore volume, 24 weeks Bone tissue grows into the 9% of implant pore volume, and it can be that pygostyle bone tissue is just long after being implanted into illustrate the porous hydroxyapatite Enter to create good growing environment.
Embodiment 2
Insertion between the vestibule and vestibule of the porous hydroxyapatite of the present embodiment, the vestibule of porous hydroxyapatite with it is outer Boundary is also insertion, and the aperture of the vestibule of porous hydroxyapatite is 300 μm -500 μm, and porosity 56%, preparation method is similar Immersed 7 times when embodiment 1, wherein soaking paste operate.
With reference to the same method test of embodiment 1, the porous hydroxyapatite plateau stress stage in the embodiment that obtains ties It is 0.2 × 10 that unit volume, which absorbs energy, during beam-3 J/mm3, the ratio of percent opening and porosity is 96.5%.
New zealand white rabbit Implantation Test is carried out with reference to the same method of embodiment 1, porous hydroxyapatite is implanted into tail Vertebra, the results showed that, the defects of postoperative porous hydroxyapatite is not cracked, damaged, 12 weeks after operation bone tissue grows into 70%, 14 weeks bone tissues grow into 86%, and osteanagenesis effect is good.
This kind of porous hydroxyapatite can be used for the small spongiosa bone implant material of load, such as frontal bone, cheekbone, skull, phalanges Deng the sparse position of cancellous bone of bone, also act as loading, discharge the carrier of gene and medicine.
Embodiment 3
The porous hydroxyapatite of the present embodiment is composite, inserts zirconium oxide(ZrO2), it is insertion between vestibule and vestibule , for the vestibule of porous hydroxyapatite with extraneous and insertion, the aperture of the vestibule of porous hydroxyapatite is 200 μm -300 μm, porosity 55%, preparation method similar embodiment 1, wherein porous hydroxyapatite powder be changed to porous hydroxyapatite powder with The mixture of zirconia powder, its weight compare hydroxylapatite powder:Zirconia powder is 7:3, the particle diameter of zirconia powder is 20nm- 30nm.Polyurethane foam aperture is 270 μm -390 μm, density 0.043g/cm3, immersed 7 times when soaking paste operates.
With reference to the same method test of embodiment 1, the porous hydroxyapatite plateau stress stage in the embodiment that obtains ties It is 0.9 × 10 that unit volume, which absorbs energy, during beam-2J/mm3, the ratio of percent opening and porosity is 96.1%.
New zealand white rabbit Implantation Test is carried out with reference to the same method of embodiment 1, porous hydroxyapatite is implanted into volume Bone, the results showed that, the defects of postoperative porous hydroxyapatite is not cracked, damaged, 12 weeks after operation bone tissue grows into 79%, 14 All bone tissues grow into 97%, and osteanagenesis effect is good.
This kind of porous hydroxyapatite composite can be used for the small spongiosa bone implant material of load, such as frontal bone, cheekbone, cranium The cancellous bone implants of the bones such as bone, phalanges.
Hydroxyapatite can also be with carbon fiber, biological glass fiber, macromolecular fibre, polylactic-co-glycolic acid, polyethers The Material claddings such as ether ketone, polyamide, ultra-high molecular weight polyethylene, PLA, graphene or zirconium dioxide, prepare porous hydroxyapatite The composite of apatite, increase its obdurability, improve energy absorption, contribute to Bone Ingrowth, biological glass fiber, poly- breast Acid etc. can promote the adhesion of cell, differentiation, accelerate Bone Ingrowth speed.

Claims (5)

1. a kind of porous hydroxyapatite, the material body of the porous hydroxyapatite is by vestibule and the cavity wall structure around vestibule Into vestibule is insertion, it is characterised in that:The porosity of the porous hydroxyapatite is not more than 90%, and unit volume absorbs energy Amount is not less than 1.08 × 10 at the end of the plateau stress stage-5 J/ mm3
2. porous hydroxyapatite as claimed in claim 1, it is characterised in that:The aperture of the porous hydroxyapatite is 200μm-500μm。
3. porous hydroxyapatite as claimed in claim 1, it is characterised in that:The percent opening of the porous hydroxyapatite with The ratio of porosity is more than 96%.
4. the porous hydroxyapatite as described in claims 1 to 3 any claim, it is characterised in that:The porous hydroxyapatite Apatite is the composite using hydroxyapatite as base material.
5. porous hydroxyapatite as claimed in claim 4, it is characterised in that:The composite is porous hydroxyapatite With zirconium dioxide, carbon fiber, biological glass fiber, macromolecular fibre, polylactic-co-glycolic acid, polyether-ether-ketone, polyamide, super The composite of High molecular weight polyethylene, PLA or graphene.
CN201610834316.XA 2016-09-20 2016-09-20 A kind of porous hydroxyapatite Pending CN107837419A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108939147A (en) * 2018-08-21 2018-12-07 佘菊芳 A kind of engineering in medicine material containing graphene

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GB2078696B (en) * 1980-05-28 1983-11-30 Mitsubishi Mining & Cement Co Filler for implanting in defects or hollow portions of bones
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US6340648B1 (en) * 1999-04-13 2002-01-22 Toshiba Ceramics Co., Ltd. Calcium phosphate porous sintered body and production thereof
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CN108939147A (en) * 2018-08-21 2018-12-07 佘菊芳 A kind of engineering in medicine material containing graphene

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Application publication date: 20180327