CN108310454A - A kind of gradient bioceramic material and preparation method thereof of cladding gelatin/chitosan composite porous film - Google Patents
A kind of gradient bioceramic material and preparation method thereof of cladding gelatin/chitosan composite porous film Download PDFInfo
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
- A61L27/222—Gelatin
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
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- A—HUMAN NECESSITIES
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/06—Materials or treatment for tissue regeneration for cartilage reconstruction, e.g. meniscus
Abstract
The present invention provides a kind of gradient bioceramic material and preparation method thereof of cladding gelatin/chitosan composite porous film, bioceramic used is gradient β type calcium polyphosphate biological ceramics, include chitosan and gelatin in complex sol, compared with gradient β types calcium polyphosphate biological ceramic, the degradation rate in Tris HCl solutions improves 2~11 times to the material.Step is simple and convenient to operate, is highly practical.
Description
Technical field
The invention belongs to bioceramic material field, more particularly to a kind of ladder of cladding gelatin/chitosan composite porous film
Spend bioceramic material and preparation method thereof.
Background technology
Articular cartilage tissue is a kind of porous permeable, two-phase, viscoelastic tissue with unique biomechanics performance, is
It is made of extracellular matrix and the cartilage cell being dispersed in matrix.Cartilaginous tissue can be divided into four parts, surface layer under cartilage
Bone photo connects, and as mechanical stress and compressive deformation caused by body fluid flowing gradually die down, body-fluid pressure enhancing causes each section
Density, the form of porosity and cartilage cell are different, are divided into surface layer, middle layer, deep layer and calcification from top to bottom
Layer.
Calcium polyphosphate (Calcium Polyphosphate, CPP) is a kind of calcium orthophosphate base inorganic polymer, its main chain
Structure is not formed by connecting by simple covalent bond, is connected by [PO3-] ion of tetrahedral structure, therefore both can be with
Using the characteristic of polymer, its performance is regulated and controled by structural parameters such as the degree of polymerization of change material；Simultaneously calcium ion with
[PO3-] is be combined with each other with ionic bond, therefore the characteristics of can also utilizing it as inorganic matter studies material.But CPP
Brittleness is big, and degradation speed is too slow, can not meet the requirement of Bone Defect Repari.And composite technology is the important way solved these problems
One of diameter.Chitosan is from chitin by a kind of deacetylated cationic polysaccharide extracted.With good life
Object degradation property, biocompatibility and bioactivity, but chitosan film layer pore volume is smaller, pore volume is for material
The degradation of material and cell adherence are all extremely important.Gelatin is hydrolyzing by extracellular matrix, is a kind of polypeptide of isomery
Object is closed, as a kind of collagen, gelatin is a kind of polyampholyte, can be with hydrone with Hydrogenbond.Gelatin does not dissolve in
Most of nonpolar organic solvent such as alcohol, but it can be dissolved in the aqueous solution of water acetic acid and some polyalcohols, chitosan is same
The weak acid solutions such as water acetic acid can be dissolved in.Meanwhile gelatin has structure similar with organism collagen, compared with its antigenicity of natural collagen
It is lower, and its catabolite is easily absorbed by human body, and without additional inflammatory reaction, and degradation speed is very fast.Hole body
Product will have a direct impact on growth and the degradation property of biological material cell, and gelatin has apparent shadow for film layer pore volume
It rings.
Invention content
In order to overcome above-mentioned deficiency, the present invention to provide a kind of gradient biology pottery of cladding gelatin/chitosan composite porous film
Ceramic material and preparation method thereof.Bioceramic used is gradient β type calcium polyphosphate biological ceramics, includes chitosan in complex sol
And gelatin, compared with gradient β types calcium polyphosphate biological ceramic, the degradation rate in Tris-HCl solution improves 2~11 times to the material.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of preparation method of the gradient bioceramic material of cladding gelatin/chitosan composite porous film, including：
1) biphosphate calcium powder is warming up to 500 DEG C with the speed of 2 DEG C/min~6 DEG C/min, preferred heating rate
For 3 DEG C/min~5 DEG C/min, further preferred heating rate is 4 DEG C/min, keeps the temperature 2~12h, preferred 6h~11h, into
The preferred 10h. of one step
Be sintered, after furnace cooling to room temperature grinding be sufficiently mixed with binder polyvinyl alcohol, ball milling, drying, sieving,
It is spare to obtain powder 1；
2) by stearic acid ball milling, filter out 50~200 mesh pore-foaming agents, preferably respectively 50~80 mesh or 80~120 mesh；
3) by powder 1 and 80~120 mesh aperture pore-foaming agents in mass ratio 1.5~4:1 preferably 3:1 ratio is uniformly mixed
Obtain powder 2, powder 1 and 50~80 mesh pore-foaming agents in mass ratio 1.5~4:1, preferably 2.5:1 is uniformly mixed as powder 3；It presses
According to ratio 1:3:7 or 1:2:8 or 1:4:6 weigh powder 1, powder 2 successively, and powder 3 is pressed into diameter 1cm with powder compressing machine,
The cylinder of high 1cm, preferred ratio are 1:3:7
4) sample of above-mentioned compacting is risen to 400 DEG C with the rate of 2 DEG C/min~6 DEG C/min, preferred heating rate is 3
DEG C/min~5 DEG C/min, further preferred heating rate is 4 DEG C/min, after keeping the temperature 2h, then is risen to the rate of 4 DEG C/min
800 DEG C~900 DEG C, preferably 850 DEG C~880 DEG C, further preferably 850 DEG C keep the temperature 60min~120min, preferably
90min。
Cool to room temperature with the furnace；Obtain gradient β type calcium polyphosphate biological ceramics.It is polished with 600# sand paper sample surfaces
Afterwards, it is cleaned by ultrasonic with alcohol, removes degreasing and remaining powder, drying.
5) gradient β type calcium polyphosphate biological ceramics surface cladding gelatin/chitosan complex sol to get cladding gelatin/
The gradient bioceramic material of chitosan composite porous film.
Preferably, viscosity≤200mPa.s chitosans and gelatin are contained in the gelatin/chitosan complex sol.
Preferably, a concentration of 3%-9% of the gelatin/chitosan complex sol, preferably 3%-6%, further
Preferably 6%, gelatin proportion 1/6~5/6, further preferably 1/3-2/3.
Preferably, step 5) the specific steps are：Pretreated matrix is dried, the complex sol prepared stands 12h
De-bubble weighs 80g complex sols and is placed in 200ml beakers, measures 8ml dibutyl phthalates and pours into colloidal sol, stirring is equal
Matrix is immersed in chitosan/gelatin-compounded colloidal sol after even, under the conditions of 40 DEG C of constant temperature water baths, impregnates 6h-48h, preferably time
For -48h for 24 hours, further preferably for 24 hours, ultrasonic vibration 10min, after taking-up under the conditions of 55 DEG C forced air drying 6h；It uses successively
0.1mol/L NaOH solutions, deionized water, acetone remove remaining acetic acid, remove pore-foaming agent dibutyl phthalate successively, drum
Wind drying box is dried.
Preferably, the gelatin/chitosan complex sol preparation method：Glacial acetic acid solution is measured, deionization is dissolved into
In water, stir evenly.Chitosan powder is weighed, is add to deionized water, being sufficiently stirred makes chitosan divide in deionized water
It dissipates uniformly, the configured acetum in front is added dropwise, stirs evenly to form chitosan colloidal sol, which is placed in 40 DEG C of items
Under part, gelatin is added, stirs evenly, forms complex sol.
Preferably, the gelatin/chitosan complex sol preparation method：
1) acetum used in is with deionized water volume ratio：2-8:50, preferably 4-6:50, further preferably 4:
50
2) mixing time is 12-90min, preferably 15-60min, further preferably 30min；
3) Chitosan powder and deionized water ratio are：2-8g:50ml, preferably 2-6g:50ml, further preferably
For 2g:50ml,3g:50ml,4g:50ml, finally preferably 3g:50ml
4) the gelatin quality is 2-8g, preferably 2-6g, further preferably 2g, 3g, 4g, is preferably finally this hair of 3g
The bright gradient bioceramic material for additionally providing cladding gelatin/chitosan composite porous film prepared by any above method.
The present invention also provides a kind of cartilage or Bone Defect Repari degradable biological timbering material, including it is above-mentioned gradient porous
Bioceramic impregnates the material of membrane formation process surface cladding chitosan/gelatine composite porous film.
The present invention also provides the gradient bioceramic materials of above-mentioned cladding gelatin/chitosan composite porous film to make
Application in bio-medical material.
Beneficial effects of the present invention
(1) the present invention provides a kind of the gradient bioceramic materials and its system of cladding gelatin/chitosan composite porous film
Preparation Method, which is characterized in that bioceramic used is gradient β type calcium polyphosphate biological ceramics, includes chitosan in complex sol
And gelatin, compared with gradient β types calcium polyphosphate biological ceramic, the degradation rate in Tris-HCl solution improves 2~20 times to the material.
(2) preparation method of the present invention is simple, efficient, highly practical, easy to spread.
Description of the drawings
The accompanying drawings which form a part of this application are used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation do not constitute the improper restriction to the application for explaining the application.
Fig. 1 is porous gelatin/chitosan composite film cladding calcium polyphosphate biological ceramic material prepared by embodiment 1,2,3
Surface topography (the chitosan solution covering material that (a) is a concentration of 6%, (b), (c), (d) be followed successively by the preparation of embodiment 1,2,3
Sample)
Fig. 2 is the sample for preparing of embodiment 1,2,3 mass change and pH variation diagram after the immersion of Tris-HCl solution.(a:
Chitosan/gelatin=2:1, b:Chitosan/gelatin=1:1,c:Chitosan/gelatin=1:2)；
Fig. 3 is that embodiment 2 prepares mass change after sample and the immersion of 6% concentration Chitosan-coated sample Tris-HCl solution
Fig. 4 is object phase change figure after Tris-HCl solution impregnates.(a1,a2:Chitosan/gelatin=2:1, b1, b2:Shell is poly-
Sugar/gelatin=1:1,c1,c2:Chitosan/gelatin=1:2.7 days：a1,b1,c1,cpp-1；14 days：a2,b2,c2,cpp-2)；
Fig. 5 is that Tris-HCl solution impregnates front and rear surfaces microscopic appearance scanning figure.(a, a1, a2:Chitosan/gelatin=2:
1, b, b1, b2:Chitosan/gelatin=1:1,c,c1,c2:Chitosan/gelatin=1:2.It does not impregnate：a,b,c；7 days：a1,b1,
c1；14 days：a2,b2,c2)；
Fig. 6 is that Tris-HCl solution impregnates front and back FTIR spectrum figure variation.(a1, a2:Chitosan/gelatin=2:
1, b1, b2:Chitosan/gelatin=1:1,c1,c2:Chitosan/gelatin=1:2.7 days：a1,b1,c1；14 days：a2,b2,c2)；
Specific implementation mode
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific implementation mode, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or combination thereof.
With reference to specific embodiment, the present invention is described further.
Embodiment 1
1) preparation of porous bio-ceramic
Ceramic raw material is calcium dihydrogen phosphate, and the pore-foaming agent of selection is stearic acid.Binder is used for polyvinyl alcohol (5%PVA)
Batch-type furnace is sintered, and selects alumina crucible.Ceramic post sintering process is divided into two steps, and the process that is pre-sintered is by biphosphate calcium powder
It pours into crucible, 5 DEG C/min is warming up to 500 DEG C, keeps the temperature 10h, cools to room temperature taking-up with the furnace.After being ground roughly with mortar according to
Mass ratio is sufficiently mixed for 5% with binder polyvinyl alcohol, pours into ball grinder, and appropriate amount of deionized water (not having powder) is added,
Ball mill, with 55 DEG C of drying in air dry oven after taking-up, grain size is filtered out with 200 mesh with 230r/h speed ball milling 1h<200 mesh
Powder 1 it is spare.By stearic acid ball milling, filter out as 50~80 mesh or 80~120 mesh；Powder 1 and 80~120 mesh apertures are caused
Hole agent in mass ratio 3:1 ratio is uniformly mixed to obtain powder 2, powder 1 and 50~80 mesh pore-foaming agents in mass ratio 2.5:1 is uniformly mixed
For powder 3；Proportionally 1:3:7 weigh powder 1, powder 2 successively, and powder 3 is pressed into diameter 1cm, high 1cm with powder compressing machine
Cylinder.The sample of compression moulding is placed on aluminium oxide ceramics pallet, bottom layer overlay alumina powder, in batch-type furnace
Middle elder generation is warming up to 400 DEG C with 5 DEG C/min, keeps the temperature 120min, is warming up to 880 DEG C again, keeps the temperature 90min, cools to room temperature with the furnace.
Sample surfaces are polished thin layer with thin 600# sand paper, after be cleaned by ultrasonic with alcohol, except degreasing and remaining
Powder, drying are for use.
2) prepared by gelatin/chitosan complex sol：
4mL glacial acetic acid solutions are measured, are dissolved into 50mL deionized waters, 30min is stirred.3g Chitosan powders are weighed, are added
Enter into 50mL deionized waters, being sufficiently stirred makes chitosan be uniformly dispersed in deionized water, by the configured acetum in front
It is added dropwise, stirring 2h forms uniform chitosan colloidal sol, under the conditions of which is placed in 40 DEG C, 3g gelatin is added, stirring is equal
It is even, form the complex sol that chitosan proportion is respectively 1/2.
3) gelatin/chitosan complex sol coats
It takes the complex sol prepared in 80g steps 2) to be placed in 200ml beakers, measures 8ml dibutyl phthalates and fall
Enter in colloidal sol, matrix is immersed in chitosan/gelatin-compounded colloidal sol after stirring evenly, under the conditions of 40 DEG C of constant temperature water baths, impregnates
For 24 hours, ultrasonic vibration 10min, after taking-up under the conditions of 55 DEG C forced air drying 6h；0.1mol/L NaOH solutions, deionization are used successively
Water, acetone remove remaining acetic acid, remove pore-foaming agent dibutyl phthalate successively, air dry oven drying.
Embodiment 2
1) preparation of porous bio-ceramic：With embodiment 1
2) prepared by gelatin/chitosan complex sol：
4mL glacial acetic acid solutions are measured, are dissolved into 50mL deionized waters, 30min is stirred.2g Chitosan powders are weighed, are added
Enter into 50mL deionized waters, being sufficiently stirred makes chitosan be uniformly dispersed in deionized water, by the configured acetum in front
It is added dropwise, stirring 2h forms uniform chitosan colloidal sol, under the conditions of which is placed in 40 DEG C, 4g gelatin is added, stirring is equal
It is even, form the complex sol that chitosan proportion is respectively 1/3.
3) gelatin/chitosan complex sol coats：With embodiment 1
Embodiment 3
1) preparation of porous bio-ceramic：With embodiment 1
2) prepared by gelatin/chitosan complex sol：
4mL glacial acetic acid solutions are measured, are dissolved into 50mL deionized waters, 30min is stirred.4g Chitosan powders are weighed, are added
Enter into 50mL deionized waters, being sufficiently stirred makes chitosan be uniformly dispersed in deionized water, by the configured acetum in front
It is added dropwise, stirring 2h forms uniform chitosan colloidal sol, under the conditions of which is placed in 40 DEG C, 2g gelatin is added, stirring is equal
It is even, form the complex sol that chitosan proportion is respectively 2/3.
3) gelatin/chitosan complex sol coats：With embodiment 1
Performance test：
1, embodiment 1,2, the 3 porous gelatin/chitosan composite films prepared coat calcium polyphosphate biological ceramic material table
Face pattern as shown in Figure 1, the chitosan solution covering material that wherein (a) is a concentration of 6%, (b), (c), (d) be followed successively by implementation
The material that example 1,2,3 is prepared.From figure 1 it appears that with the increase of gelatine content, film layer hollow volume gradually increases,
This is because caused by electrostatic interaction between gelatin and chitosan molecule.
2, embodiment 1,2, the 3 porous gelatin/chitosan composite films prepared coat calcium polyphosphate biological ceramic material, with
And uncoated calcium polyphosphate biological ceramic material is that 1g/20ml is immersed in Tris-HCl solution according to mass volume ratio, it is permanent
A water is every other day changed in 37 DEG C of tepidarium, measures the pH value of a solution.It after impregnating 3 days, 7 days, 14 days respectively, takes out, uses
Deionized water and absolute ethyl alcohol remove remained on surface ion successively, its weight is weighed after drying, obtain impregnating front and back weight-loss ratio.
Weight-loss ratio of Fig. 2 porous gelatin/chitosan composite film cladding calcium polyphosphate biological ceramic materials in Tris-HCl solution with
PH value variation in the comparison of calcium polyphosphate biological ceramic weight-loss ratio and soaking process.Since impregnating the 7th day, chitosan/bright
Glue ratio is 1:The material weightlessness of 1 gained is particularly evident, and after impregnating 14 days, the highest degradation rate of composite ceramic material is
5.33%, the 0.48% of pure calcium polyphosphate biological ceramic is compared, degradation rate improves 11 times.It can see in soaking process,
PH value changes between 7.2~7.4 always, it is known that in degradation process, is able to maintain that under to the advantageous mild alkaline conditions of human body.
3, porous gelatin/chitosan composite film prepared by Fig. 3 embodiments 2 coats calcium polyphosphate biological ceramic material, with
And weight-loss ratio of the calcium polyphosphate material in Tris-HCl solution is coated for a concentration of 6% chitosan solution, after impregnating 14 days,
The highest degradation rate of composite ceramic material is 5.33%, compared to the 4.16% of the bioceramic of cladding comparable sodium chitosan, drop
It solves rate and improves 1.28 times.
4, porous gelatin/chitosan composite film prepared by Fig. 4 embodiments 1,2,3 coats calcium polyphosphate biological ceramic material
It is impregnated 7 days in Tris-HCl solution, (a1:Chitosan/gelatin=2:1, b1:Chitosan/gelatin=1:1,c1:Chitosan/gelatin
=1:2) 14 days (a2:Chitosan/gelatin=2:1, b2:Chitosan/gelatin=1:1,c2:Chitosan/gelatin=1:2) object phase afterwards
Variation
5, Fig. 5 Tris-HCl solution impregnates front and rear surfaces microscopic appearance scanning figure.It impregnates 7 days, (a1:Chitosan/gelatin=
2:1, b1:Chitosan/gelatin=1:1,c1:Chitosan/gelatin=1:2)；(a2 after 14 days:Chitosan/gelatin=2:1, b2:Shell
Glycan/gelatin=1:1,c2:Chitosan/gelatin=1:2).After impregnating 7 days, the surfaces a are attached with tablet, and stick is adhered on the surfaces c
Shape object, after impregnating 14 days, the tablet on the surfaces a is degraded into smaller particle, and the club on the surfaces c is split into the needle of cluster
Shape object.And b can see the growth with soaking time, superficial film is gradually degraded, when impregnating 7 days, close to film layer position
The ceramic particle degradation set becomes smaller, this is because chitosan and colloidal sol all have certain swelling ratio, can accelerate water and solution
Effect of the intermediate ion to calcium polyphosphate particle.
6, Fig. 6 Tris-HCl solution impregnates front and back FTIR spectrum figure variation.(a is not impregnated:Chitosan/gelatin=
2:1, b:Chitosan/gelatin=1:1,c:Chitosan/gelatin=1:2)；It impregnates 7 days, (a1:Chitosan/gelatin=2:1, b1:Shell
Glycan/gelatin=1:1,c1:Chitosan/gelatin=1:2)；14 days (a2:Chitosan/gelatin=2:1, b2:Chitosan/gelatin=
1:1,c2:Chitosan/gelatin=1:2)；As soaking time increases, it is located at 3400cm-1It is formed about-the OH's of hydrogen bond association
Stretching vibration peak becomes narrow gradually, and chitosan before explanation, there are Hyarogen-bonding reductions between gelatin and calcium polyphosphate.P-O-P,
And 1100cm-1Neighbouring P-O weakens.
Finally it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not limited to this hair
It is bright, although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still
It can modify to the technical solution recorded in previous embodiment, or equivalent replacement is carried out to which part.It is all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not to the scope of the present invention
Limitation, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not required to
Make the creative labor the various modifications or changes that can be made still within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of the gradient bioceramic material of cladding gelatin/chitosan composite porous film, which is characterized in that institute
The purer bioceramic of gradient bioceramic material degradation rate for stating glue/chitosan composite porous film clearly improves 2-11 times.
2. such as the above-mentioned method of claim 1, which is characterized in that gradient β type calcium polyphosphate biological ceramics surface coat gelatin/
Chitosan complex sol contains viscosity 50-200mPa.s chitosans and gelatin in the gelatin/chitosan complex sol.
3. such as the above-mentioned method of claim 1, which is characterized in that the concentration 3%-9% of the gelatin/chitosan complex sol,
Preferably 3%-6%, further preferably 6%, gelatin proportion 1/6~5/6, preferably 1/3-2/3, further preferably
It is 1/2.
4. such as the above-mentioned method of claim 2, which is characterized in that the specific steps are：Pretreated matrix drying, what is prepared answers
It closes colloidal sol and stands 12h de-bubbles, weigh 80g complex sols and be placed in 200ml beakers, measure 8ml dibutyl phthalates and pour into
In colloidal sol, matrix is immersed in chitosan/gelatin-compounded colloidal sol after stirring evenly, under the conditions of 40 DEG C of constant temperature water baths, impregnates 6h-
48h, preferably time are -48h for 24 hours, and further preferably for 24 hours, ultrasonic vibration 10min, air blast is dry under the conditions of 55 DEG C after taking-up
Dry 6h；0.1mol/L NaOH solutions, deionized water, acetone is used to remove remaining acetic acid successively, remove pore-foaming agent O-phthalic successively
Dibutyl phthalate, air dry oven drying.
5. the method as described in claim 1, which is characterized in that the gelatin/chitosan complex sol preparation method：It measures
Glacial acetic acid solution is dissolved into deionized water, is stirred evenly.Chitosan powder is weighed, is add to deionized water, is sufficiently stirred
So that chitosan is uniformly dispersed in deionized water, the configured acetum in front is added dropwise, stirs evenly to form chitosan
Colloidal sol under the conditions of the colloidal sol is placed in 40 DEG C, is added gelatin, stirs evenly, forms complex sol.
Preferably, the gelatin/chitosan complex sol preparation method：
1) acetum used in is with deionized water volume ratio：2-8:50, preferably 4-6:50, further preferably 4:50
2) mixing time is 12-90min, preferably 15-60min, further preferably 30min；
3) Chitosan powder and deionized water ratio are：2-8g:50ml, preferably 2-6g:50ml, further preferably
2g:50ml,3g:50ml,4g:50ml, finally preferably 3g:50ml；
4) the gelatin quality is 2-8g, preferably 2-6g, further preferably 2g, 3g, 4g, finally preferably 3g.
6. the gradient bioceramic material of cladding gelatin/chitosan composite porous film as described in claim 1, which is characterized in that
Including：
1) biphosphate calcium powder is warming up to 500 DEG C with the speed of 2 DEG C/min~6 DEG C/min, preferred heating rate is 3
DEG C/min~5 DEG C/min, further preferred heating rate is 4 DEG C/min, keeps the temperature 2~12h, preferred 6h~11h, further
Preferred 10h.
It is sintered, grinds after furnace cooling to room temperature and be sufficiently mixed with binder polyvinyl alcohol, ball milling drying, is sieved, obtains powder
Expect that 1 is spare；
2) by stearic acid ball milling, filter out 50~200 mesh pore-foaming agents, preferably respectively 50~80 mesh or 80~120 mesh；
3) by powder 1 and 80~120 mesh aperture pore-foaming agents in mass ratio 1.5~4:1 preferably 3:1 ratio is uniformly mixed to obtain powder
Material 2, powder 1 and 50~80 mesh pore-foaming agents in mass ratio 1.5~4:1, preferably 2.5:1 is uniformly mixed as powder 3；According to than
Example 1:3:7 or 1:2:8 or 1:4:6 weigh powder 1, powder 2 successively, and powder 3 is pressed into diameter 1cm, high 1cm with powder compressing machine
Cylinder, preferred ratio be 1:3:7
4) sample of above-mentioned compacting being risen to 400 DEG C with the rate of 2 DEG C/min~6 DEG C/min, preferred heating rate is 3 DEG C/
Min~5 DEG C/min, further preferred heating rate are 4 DEG C/min, after keeping the temperature 2h, then with the rate of 4 DEG C/min rise to 800
DEG C~900 DEG C, preferably 850 DEG C~880 DEG C, further preferably 850 DEG C keep the temperature 60min~120min, preferably 90min.
Cool to room temperature with the furnace；Obtain gradient β type calcium polyphosphate biological ceramics.After being polished with 600# sand paper sample surfaces,
It is cleaned by ultrasonic with alcohol, removes degreasing and remaining powder, drying.
7. the gradient bioceramic of cladding gelatin/chitosan composite porous film prepared by any one of claim 1-6 the methods
Material.
8. a kind of cartilage or Bone Defect Repari degradable biological timbering material, which is characterized in that including the gradient described in claim 7
Porous bio-ceramic impregnates the material of membrane formation process surface cladding gelatin/chitosan composite porous film.
9. the gradient bioceramic material of the cladding gelatin/chitosan composite porous film described in claim 7 is making biology doctor
With the application in material.
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