CN105920673B - Complex phase porous stent structure preparation method based on temperature regulation complex phase apatite ingredient - Google Patents

Complex phase porous stent structure preparation method based on temperature regulation complex phase apatite ingredient Download PDF

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Publication number
CN105920673B
CN105920673B CN201610329235.4A CN201610329235A CN105920673B CN 105920673 B CN105920673 B CN 105920673B CN 201610329235 A CN201610329235 A CN 201610329235A CN 105920673 B CN105920673 B CN 105920673B
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complex phase
temperature
hydroxyapatite
ingredient
tcp
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CN201610329235.4A
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CN105920673A (en
Inventor
饶群力
饶曼琦
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
    • A61L27/425—Composite 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
    • 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
    • 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
    • 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
    • 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
    • A61L27/58—Materials at least partially resorbable by the body
    • 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

Abstract

A kind of complex phase porous stent structure preparation method based on temperature regulation complex phase apatite ingredient, hydroxyapatite, polymethyl methacrylate, lauryl sodium sulfate are uniformly mixed, ammonium bicarbonate soln is instilled to stir evenly, it is heated and is kept the temperature after to be dried, the modulation that complex phase apatite ingredient is realized finally by the temperature of control heat preservation, that is, the temperature height kept the temperature are proportional with the content of α-TCP complex phase ingredient in complex phase apatite.Present invention process is not necessarily to ball milling, and what is obtained after heat treatment is hydroxyapatite and α-TCP complex phase ingredient, and the biology performance for the bracket being prepared is good, is the optimal selection for substituting human body and being damaged sclerous tissues.

Description

Complex phase porous stent structure preparation method based on temperature regulation complex phase apatite ingredient
Technical field
It is specifically a kind of that complex phase phosphorus is regulated and controled based on temperature the present invention relates to a kind of technology of field of biomedical materials The complex phase porous stent structure preparation method of lime stone ingredient.
Background technique
Hydroxyapatite is the main inorganic composition of skeleton and tooth, thus has good bioactivity, and bone lures The property led.Porous hydroxyapatite not only has the characteristic of hydroxyapatite, also has criss-cross hole, promotes nutriment The discharge of input and metabolin, to induce osteocyte apposition growth, accelerate new bone formation, repair skeletal tissue deficiencies.System at present The method of standby porous material has template, freeze-drying, foaming, addition pore creating material method etc..
Summary of the invention
The present invention must post-process template for the prior art, complex process, and the main component in finished product is Many technological deficiencies such as hydroxyapatite propose a kind of complex phase porous stent structure based on temperature regulation complex phase apatite ingredient Preparation method is not necessarily to ball milling, and what is obtained after heat treatment is hydroxyapatite and α-TCP complex phase ingredient, the bracket being prepared Biology performance it is good, be substitute human body be damaged sclerous tissues optimal selection.
The present invention is achieved by the following technical solutions:
The present invention relates to a kind of complex phase porous stent structure preparation methods based on temperature regulation complex phase apatite ingredient, will Hydroxyapatite, polymethyl methacrylate (PMMA), lauryl sodium sulfate (SDS) uniformly mix, and it is molten to instill ammonium hydrogen carbonate Liquid stirs evenly, and is heated and is kept the temperature after to be dried, realizes complex phase apatite ingredient finally by the temperature of control heat preservation Modulation.
The heating, temperature are preferably 600~1000 DEG C.
The heating, heating rate are preferably 2 DEG C/min~4 DEG C/min.
The heat preservation, time are preferably 3~6 hours.
The heat preservation is further preferably first warming up to 600 DEG C with 4 DEG C/min and keeps the temperature 1 hour, then with 2 DEG C/min liter Temperature to 800~900 DEG C keep the temperature 3~5 hours.
The modulation refers to: the temperature height of heat preservation is proportional with the content of α-TCP complex phase ingredient in complex phase apatite.
The modulation, the content such as following table of the α-TCP complex phase ingredient preferably obtained after corresponding temperature is kept the temperature 3 hours It is shown:
Ratio holding temperature 800℃ 850℃ 900℃ 950℃ 1000℃
α-TCP (wt%) < 5% 32~38% 40~46% 49~51% 51~52%
The method specifically includes the following steps:
Step 1, hydroxyapatite, PMMA, SDS, ammonium hydrogen carbonate are successively weighed；
Step 2, hydroxyapatite, PMMA and SDS are put into container, mechanical stirring is uniform；
Step 3, ammonium hydrogen carbonate is dissolved in ultrapure water；
Step 4, ammonium bicarbonate soln is instilled in the powder mixed, is again stirring for uniformly；
Step 6, it is put into baking oven drying, block is taken out after drying, is put into crucible；
Step 7, crucible is put into high temperature furnace, is kept the temperature after being warming up to 600~1000 DEG C；
Step 8, crucible is taken out after furnace cooling, obtains hydroxyapatite and α-TCP complex phase porous support.
The hydroxyapatite, is preferably prepared by chemical precipitation method, specifically: by Calcium diacetate monohydrate (Ca (CH3COO)2·H2) and potassium dihydrogen phosphate (KH O2PO4) be dissolved in high purity water respectively；Then two kinds are adjusted with potassium hydroxide solution PH value of solution is to 7；Two hydration potassium fluoride (KF2H are taken again2O it) is dissolved in potassium dihydrogen phosphate, by KH2PO4It is molten with the mixing of KF Liquid is added drop-wise to Ca (CH with the speed of 0.1mL/s3COO)2In solution, while completely cutting off air using preservative film, avoids CO2It participates in anti- It answers.Electromagnetic agitation 4h dries under the conditions of 80 DEG C after being aged a night, obtains hydroxyapatite.
The present invention relates to the complex phase porous supports based on temperature regulation complex phase apatite ingredient that the above method is prepared Structure, component and content are as follows: hydroxyapatite and α-TCP complex phase, wherein the content of α-TCP (wt%) is (0,52wt%).
The hydroxyapatite is the fluorination hydroxyapatite that fluorine replaces part of hydroxyl, and α-TCP is with monoclinic crystal Structure, molecular formula Ca3(PO4)2Compound.
The present invention relates to the applications of above-mentioned complex phase porous stent structure, particularly for making artificial bone tissue.
Technical effect
Compared with prior art, any template is not used in the present invention, and bracket is hydroxyapatite and α-TCP complex phase ingredient. Process flow is simple, easily operated.Since α-TCP is more excellent compared to hydroxyapatite and β-TCP biological property, so of the invention Complex phase porous support biocompatibility and biological degradability be better than simple hydroxyapatite scaffold or hydroxyapatite and β- TCP two-phase bracket, may be selected as bone alternate material of new generation.
Detailed description of the invention
Fig. 1 is the XRD spectra for the complex phase apatite porous support that the embodiment of the present invention 1 synthesizes；
Fig. 2 is the XRD spectra for the complex phase apatite porous support that the embodiment of the present invention 2 synthesizes；
Fig. 3 is the XRD spectra for the complex phase apatite porous support that the embodiment of the present invention 3 synthesizes.
Specific embodiment
Embodiment 1
The present embodiment the following steps are included:
Step 1, apatite, PMMA, SDS and ammonium hydrogen carbonate are weighed by 8:6:11:3 weight ratio；
Step 2, hydroxyapatite, PMMA and SDS are put into glass container, it is uniform with mechanical stirring；
Step 3, ammonium hydrogen carbonate is dissolved in ultrapure water by 1:1；
Step 4, ammonium bicarbonate soln is instilled in the powder mixed, is stirred evenly；
Step 6, it is put into baking oven, 70 DEG C of drying are taken out block after drying, are put into crucible；
Step 7, crucible is put into high-temperature heater, 4 DEG C/min is warming up to 600 DEG C and keeps the temperature 0.5 hour；
Step 8, continue to be warming up to 800 DEG C of heat preservations 3 hours with 2 DEG C/min；
Step 9, crucible is taken out after furnace cooling, obtains the porous of hydroxyapatite and α-TCP (< 5wt%) complex phase ingredient Bracket.
The XRD spectra that the present embodiment is related to the product that the above method is prepared is as shown in Figure 1.
For the present embodiment using the apatite of fluorine part substituted hydroxy as main phase, thermal stability is better than common hydroxyapatite.
Embodiment 2
The present embodiment the following steps are included:
Step 1, hydroxyapatite, PMMA, SDS and ammonium hydrogen carbonate are weighed by 8:6:11:3 weight ratio；
Step 2, hydroxyapatite, PMMA and SDS are put into glass container, it is uniform with mechanical stirring；
Step 3, ammonium hydrogen carbonate is dissolved in ultrapure water by 1:1；
Step 4, ammonium bicarbonate soln is instilled in the powder mixed, is stirred evenly；
Step 6, it is put into baking oven, 70 DEG C of drying are taken out block after drying, are put into crucible；
Step 7, crucible is put into high-temperature heater, 4 DEG C/min is warming up to 600 DEG C and keeps the temperature 0.5 hour；
Step 8, continue to be warming up to 860 DEG C of heat preservations 5 hours with 2 DEG C/min；
Step 9, crucible is taken out after furnace cooling, obtains the porous of hydroxyapatite (58%) and α-TCP (42%) complex phase Bracket.
The XRD spectra that the present embodiment is related to the product that the above method is prepared is as shown in Figure 2.
The present embodiment is better than HA by two phase composition of hydroxyapatite and α-TCP, biocompatibility and biological degradability With β-TCP two-phase blend, wherein α-TCP mutually has good osteoconductive and osteoinductive, has in bone tissue engineer field Application prospect.
Embodiment 3
The present embodiment the following steps are included:
Step 1, hydroxyapatite, PMMA, SDS and ammonium hydrogen carbonate are weighed by 8:6:11:3 weight ratio；
Step 2, hydroxyapatite, PMMA and SDS are put into glass container, it is uniform with mechanical stirring；
Step 3, ammonium hydrogen carbonate is dissolved in ultrapure water by 1:1；
Step 4, ammonium bicarbonate soln is instilled in the powder mixed, is stirred evenly；
Step 6, it is put into baking oven, 70 DEG C of drying are taken out block after drying, are put into crucible；
Step 7, crucible is put into high-temperature heater, 4 DEG C/min is warming up to 600 DEG C and keeps the temperature 1 hour；
Step 8, continue to be warming up to 900 DEG C of heat preservations 4 hours with 2 DEG C/min；
Step 9, crucible is taken out after furnace cooling, obtained by the more of hydroxyapatite (55%) and α-TCP (45%) complex phase Hole bracket.
The XRD spectra that the present embodiment is related to the product that the above method is prepared is as shown in Figure 3.
The present embodiment α-TCP phase proportion quantity increases, and biological degradability is better than preceding two embodiment, is implanted into after human body instead Should be mild, degradation is easy to absorb rapidly, and not will cause local soda acid sexual maladjustment, is high-quality bone alternate material.
Above-mentioned specific implementation can by those skilled in the art under the premise of without departing substantially from the principle of the invention and objective with difference Mode carry out local directed complete set to it, protection scope of the present invention is subject to claims and not by above-mentioned specific implementation institute Limit, each implementation within its scope is by the constraint of the present invention.

Claims (6)

1. a kind of complex phase porous stent structure preparation method based on temperature regulation complex phase apatite ingredient, which is characterized in that will Hydroxyapatite, polymethyl methacrylate, lauryl sodium sulfate uniformly mix, and instill ammonium bicarbonate soln and stir evenly, It is heated and is kept the temperature after to be dried, the modulation of complex phase apatite ingredient is realized finally by the temperature of control heat preservation, that is, is kept the temperature Temperature height it is proportional with the content of α-TCP complex phase ingredient in complex phase apatite；
The heating and heat preservation, it is specific to be first warming up to 600 DEG C with 4 DEG C/min and keep the temperature 1 hour, then 800 are warming up to 2 DEG C/min ~900 DEG C keep the temperature 3~5 hours.
2. preparation method according to claim 1, characterized in that the modulation refers to: keeping the temperature 3 hours in corresponding temperature The content of the α-TCP complex phase ingredient obtained afterwards is as shown in the table
3. preparation method according to claim 1 or 2, characterized in that the method specifically includes the following steps:
Step 1, hydroxyapatite, PMMA, SDS, ammonium hydrogen carbonate are successively weighed；
Step 2, hydroxyapatite, PMMA and SDS are put into container, mechanical stirring is uniform；
Step 3, ammonium hydrogen carbonate is dissolved in ultrapure water；
Step 4, ammonium bicarbonate soln is instilled in the powder mixed, is again stirring for uniformly；
Step 6, it is put into baking oven drying, block is taken out after drying, is put into crucible；
Step 7, crucible is put into high temperature furnace, is warming up to 600 DEG C of heat preservations, then 800~900 DEG C of heat preservations are warming up to 2 DEG C/min；
Step 8, crucible is taken out after furnace cooling, obtains hydroxyapatite and α-TCP complex phase porous support.
4. preparation method according to claim 3, characterized in that the hydroxyapatite, especially by following manner It is prepared: Calcium diacetate monohydrate and potassium dihydrogen phosphate is dissolved in high purity water respectively；Then two are adjusted with potassium hydroxide solution PH value of solution is planted to 7；Two hydration potassium fluorides are taken to be dissolved in potassium dihydrogen phosphate again, by KH2PO4With the mixed solution of KF, with The speed of 0.1mL/s is added drop-wise to Ca (CH3COO)2In solution, while completely cutting off air using preservative film, avoids CO2Participate in reaction, electricity Magnetic stirs 4h, after being aged a night, dries under the conditions of 80 DEG C, obtains hydroxyapatite.
5. a kind of complex phase porous stent structure being prepared according to any of the above-described claim the method, which is characterized in that Component and content are as follows: hydroxyapatite and α-TCP complex phase, wherein the mass percentage content of α-TCP is (0,52%).
6. it is a kind of according to claim 1~4 in the application of complex phase porous stent structure that is prepared of any the method, it is special Sign is, is used for making artificial bone tissue.
CN201610329235.4A 2016-05-18 2016-05-18 Complex phase porous stent structure preparation method based on temperature regulation complex phase apatite ingredient Expired - Fee Related CN105920673B (en)

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WO2021189435A1 (en) * 2020-03-27 2021-09-30 苏州信和隆医疗器械有限公司 Novel calcium phosphate composite active material having core-shell structure and preparation method therefor

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CN102942358B (en) * 2012-11-21 2014-08-27 上海交通大学 Preparation method of fluorinated hydroxyapatite (HA) composite material with uniform porous structure
CN103170006A (en) * 2013-04-12 2013-06-26 上海交通大学 Method for preparing porous hydroxyapatite scaffold via two-step process
CN103341213B (en) * 2013-06-25 2015-06-24 上海交通大学 Preparation method for FHA/beta-TCP (fluorhydroxyapatite/beta-tertiary calcium phosphate) diphasic fluoridated hydroxyapatite 3D (three-dimensional) porous scaffold

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