CN102604146A - Inorganic bioactive material and method for preparing polymer porous composite material - Google Patents
Inorganic bioactive material and method for preparing polymer porous composite material Download PDFInfo
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- CN102604146A CN102604146A CN2012100746658A CN201210074665A CN102604146A CN 102604146 A CN102604146 A CN 102604146A CN 2012100746658 A CN2012100746658 A CN 2012100746658A CN 201210074665 A CN201210074665 A CN 201210074665A CN 102604146 A CN102604146 A CN 102604146A
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Abstract
The invention discloses an inorganic bioactive material and a method for a polymer porous composite material. The method comprises the following steps of: selecting a pore-forming agent with required particle size; mixing the inorganic bioactive material, polymer, an organic solvent and the pore-forming agent; placing an obtained mixture into a die and carrying out curing; and removing the pore-forming agent to obtain the porous composite material. According to the invention, a die plate and the pore-forming agent can be synthesized and formed in one step by pressurization and polymerization; the process is simple; the uniformity and the continuity of pores are ensured; and a good environment can be provided for subsequent cell growth and tissue neogenesis. Moreover, the prepared material has certain elasticity and has good ductility.
Description
Technical field
The present invention relates to composite porous preparation, the preparation method of particularly a kind of inorganic bioactivity material and polyalcohol stephanoporate matrix material.
Background technology
Win 40350 (HAP) has good biocompatibility, is the important component part of bone and tooth.Win 40350 is similar with the inorganic components of skeleton, and nontoxic, has excellent biological compatibility and biological activity, has the performance of guiding skeletonization.But in as bone alternate material, also there is the deficiency of self in HAP, and for example mechanical property is relatively poor etc., thereby has limited its application.
Bio-vitric is the glass that can realize specific biological function, is placed in the physiological solution, can induce the formation Win 40350, so in the implant into body, can repair osseous tissue, has bone conduction, bone and effect such as induces.
Inorganic bios such as the polymer materials of good mechanical properties and HAP, bio-vitric is compound, just can obtain the multifunctional composite that biocompatibility and mechanical property have concurrently.With isolated cells; Through planting in cytoskeleton behind the cultured and amplified in vitro or claiming on the extracellular matrix; This biomaterial scaffolds can be the three-dimensional space that cell provides existence, helps cell and obtains enough nutritive substances, carries out gaseous interchange; Get rid of waste material, cell is grown on the three-dimensional rack of prefabricated form.Mostly we are the hole material by prepared biomaterial, and the structure of imitation ground substance of bone is with the growth of control cell, the conveying of nutritive substance etc.Above-mentioned Composite Preparation is become porous material, make it be expected to be applied to cytoskeleton, be used to study cell growth, the conveying of nutritive substance and the influence of extraneous mechanical stimulation cell growth etc.The preparation of porous biomaterial, key are to realize the control of pore texture and the requirement of satisfying mechanical property.
Summary of the invention
Present composite porous technology of preparing is more; Be separated etc. like foaming, thermic, but the homogeneity in all difficult control aperture, and existing pore-forming material method is not all stressed the homogeneous of particle diameter; And generally be to carry out the salt template earlier in building-up process; Strengthen connectedness with high humidity micro dissolution salt grain surface then, grouting at last is synthetic, complex process.
The technical problem that the present invention will solve proposes the preparation method of a kind of inorganic bioactivity material and polyalcohol stephanoporate matrix material exactly, to overcome existing composite porous hole fabrication techniques complex process, is difficult to control the problem of aperture homogeneous.
In order to address the above problem, the present invention provides the preparation method of a kind of inorganic bioactivity material and polyalcohol stephanoporate matrix material, comprising:
Step 1 is selected the pore-forming material of required particle diameter;
Step 2 is mixed inorganic bioactivity material, polymkeric substance and organic solvent with pore-forming material;
Step 3, the mixture that step 2 is obtained places mould, is cured;
Step 4 is removed pore-forming material, obtains composite porous.
Preferably, above-mentioned preparation method also has following characteristics:
In the said step 1, select before the pore-forming material of required particle diameter, earlier pore-forming material is sieved into different particle diameters.
Preferably, above-mentioned preparation method also has following characteristics:
Selected pore diameter range is 50 μ m-1000 μ m.
Preferably, above-mentioned preparation method also has following characteristics:
Before said step 2, also comprise: said inorganic bioactivity material is dried in baking oven.
Preferably, above-mentioned preparation method also has following characteristics:
In said step 3, heating through the mixture that step 2 is obtained is cured, and perhaps, said mixture is added gentle pressurization be cured, and the temperature that wherein is cured is 60-130 ℃, and pressure is 0-100N, and the time is 30 minutes-2 hours.
Preferably, above-mentioned preparation method also has following characteristics:
In the said step 4, be soaked in the deionized water, carry out supersound process, pore-forming material is fully dissolved, thereby remove pore-forming material through the solidified mixture that step 3 is obtained.
Preferably, above-mentioned preparation method also has following characteristics:
Said polymkeric substance can be in Vilaterm (PE), POLYACTIC ACID (PLA), polymethylmethacrylate (PMMA), chitosan (CS), Zylox (SR), polyamide (PA), the Z 150PH (PVA) etc. one or more.
Preferably, above-mentioned preparation method also has following characteristics:
Said inorganic bioactivity material can be one or more in Win 40350, bio-vitric, calcium phosphate, Lin Suanergai, tricalcium phosphate, TTCP, the fluorapatite etc.
Preferably, above-mentioned preparation method also has following characteristics:
Said pore-forming material can be in sodium-chlor (NaCl) particle, Repone K (KCl) particle, calcium chloride (CaCl2) particle, paraffin particles, sucrose granules, sodium hydroxide (NaOH) particle etc. one or more.
Preferably, above-mentioned preparation method also has following characteristics:
Said organic solvent can be silicone oil, ethanol etc.
The present invention can be with the once synthetic moulding of template-pore-forming material through pressure polymerization, and technology is simple, and has guaranteed the homogeneity in hole, connectedness, and can give provides good environment to follow-up cell growth, tissue new life.And the material of preparation has certain elasticity, and ductility is good.
Description of drawings
Fig. 1 is preparing method's the schematic flow sheet of inorganic bioactivity material and the polyalcohol stephanoporate matrix material of the embodiment of the invention;
Fig. 2 is SEM (scanning electron microscopy, the scanning electron microscopy) figure after the prepared porous material of the embodiment of the invention is handled in SBF (simulated body fluid) solution.
Embodiment
Hereinafter will combine accompanying drawing that embodiments of the invention are elaborated.Need to prove that under the situation of not conflicting, embodiment among the application and the characteristic among the embodiment be arbitrary combination each other.
Core concept of the present invention is, can be through pressure polymerization with the once synthetic moulding of template-pore-forming material, and operating procedure is simple like this, and has guaranteed the homogeneity and the connectedness in hole.
As shown in Figure 1, the inorganic bioactivity material of the embodiment of the invention and the preparation method of polyalcohol stephanoporate matrix material comprise the steps:
Wherein, in above-mentioned steps 101, before the pore-forming material of selecting required particle diameter, can be through with sieve pore-forming material being sieved into different particle diameters earlier.Preferred pore diameter range is generally 50 μ m-1000 μ m.
Before said step 102, also can comprise: said inorganic bioactivity material is dried in baking oven.
In said step 102; The content of inorganic bioactivity material; The ratio of (inorganic materials/(inorganic materials+polymkeric substance)) is 0-50%, and the mass ratio of organic solvent and polymkeric substance is generally 1: 1, and the mass ratio of pore-forming material and mixture can be 1: 1,2: 1,3: 1 or the like.
In said step 103, heating through the mixture that step 102 is obtained is cured, and perhaps, said mixture is added gentle pressurization be cured, and the temperature that wherein is cured is 60-130 ℃, and pressure is 0-100N, and the time is 30 minutes-2 hours.General optional 80 ℃, 50N, 2 hours.
In the said step 104, be soaked in the deionized water, carry out supersound process, pore-forming material is fully dissolved, thereby remove pore-forming material through the solidified mixture that step 103 is obtained.
Said polymkeric substance can be in Vilaterm (PE), POLYACTIC ACID (PLA), polymethylmethacrylate (PMMA), chitosan (CS), Zylox (SR), polyamide (PA), the Z 150PH (PVA) etc. one or more.
Said inorganic bioactivity material can be one or more in HAP, bio-vitric, calcium phosphate, Lin Suanergai, tricalcium phosphate, TTCP, the fluorapatite etc.
Said pore-forming material can be sodium-chlor (NaCl) particle, Repone K (KCl) particle, calcium chloride (CaCl
2) in particle, paraffin particles, sucrose granules, sodium hydroxide (NaOH) particle etc. one or more.
Requirement to pore-forming material: nontoxic, can not react with other components of matrix material, satisfy uniform particle diameter, regular shape.
Said organic solvent can be silicone oil, ethanol etc.
Introduce composite porous porosity and mechanical property below:
The shape of hole depends on the shape of pore-forming material, and porosity depends on the quantity of pore-forming material.Porosity can obtain through fluid-discharge therapy, SEM method.Porosity ranges is 0-90%.
The measurement method of porosity method
With the W that weighs after the material oven dry
0, put into ultrapure water again and soak, vacuumize, after for some time sample is taken out, blot surface-moisture with filter paper, W weighs
1
Porosity is calculated by following formula:
Wherein, V is the volume of the sample that measures.
Composite porous ultimate compression strength reduces with the increase of porosity.Flexural strength is 20-60Mpa, and tensile strength is 0.07-10Mpa, and modulus is 2-1500Mpa.
With the example that is prepared as of the multi-functional composite porous material of HAP-PDMS--NaCl, further specify implementation process of the present invention below:
Step 1, the NaCl particle is divided into different-grain diameter with sieve, and (particle diameter is 0-50 μ m, 50-150 μ m.150-300 μ m, 300-450 μ m), select NaCl particle and the oven dry of particle diameter 150-300 μ m;
Step 2 is dried HAP in baking oven;
Step 3, PDMS, HAP, NaCl particle, silicone oil were according to 1: 1: 2: 1 mass ratio mixes;
Step 4 places mould with said mixture, pressurization (50N) heat (80 ℃) carry out solidifying in 2 hours;
Step 5 is soaked in solidified PDMS-HAP-NaCl in the deionized water, and supersound process makes salt fully dissolve (adopt usually and whenever changed water once at a distance from 2 hours, generally needed all to dissolve in 12 hours-1 day);
Step 6 obtains the PDMS-HAP porous material.
Except the multi-functional composite porous material of above-mentioned HAP-PDMS--NaCl, bio-vitric/PDMS multifunctional composite, outside bio-vitric, the HAP/PDMS multifunctional composite, this method also is applicable to other matrix materials and composite porous material.
As shown in Figure 2, be the SEM figure of prepared porous material after in SBF solution, handling, visible its inwall grows the HAP crystal, explains that it has excellent biological compatibility, to follow-up cell growth, tissue are newborn good environment is provided.
The above is merely the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of inorganic bioactivity material and polyalcohol stephanoporate matrix material comprises:
Step 1 is selected the pore-forming material of required particle diameter;
Step 2 is mixed inorganic bioactivity material, polymkeric substance and organic solvent with pore-forming material;
Step 3, the mixture that step 2 is obtained places mould, is cured;
Step 4 is removed pore-forming material, obtains composite porous.
2. preparation method as claimed in claim 1 is characterized in that,
In the said step 1, select before the pore-forming material of required particle diameter, earlier pore-forming material is sieved into different particle diameters.
3. preparation method as claimed in claim 1 is characterized in that,
Selected pore diameter range is 50 μ m-1000 μ m.
4. preparation method as claimed in claim 1 is characterized in that,
Before said step 2, also comprise: said inorganic bioactivity material is dried in baking oven.
5. preparation method as claimed in claim 1 is characterized in that,
In said step 3, heating through the mixture that step 2 is obtained is cured, and perhaps, said mixture is added gentle pressurization be cured, and the temperature that wherein is cured is 60-130 ℃, and pressure is 0-100N, and the time is 30 minutes-2 hours.
6. preparation method as claimed in claim 1 is characterized in that,
In the said step 4, be soaked in the deionized water, carry out supersound process, pore-forming material is fully dissolved, thereby remove pore-forming material through the solidified mixture that step 3 is obtained.
7. like any described preparation method in the claim 1～6, it is characterized in that,
Said polymkeric substance can be in Vilaterm (PE), POLYACTIC ACID (PLA), polymethylmethacrylate (PMMA), chitosan (CS), Zylox (SR), polyamide (PA), the Z 150PH (PVA) etc. one or more.
8. like any described preparation method in the claim 1～6, it is characterized in that,
Said inorganic bioactivity material can be one or more in Win 40350, bio-vitric, calcium phosphate, Lin Suanergai, tricalcium phosphate, TTCP, the fluorapatite etc.
9. like any described preparation method in the claim 1～6, it is characterized in that,
Said pore-forming material can be sodium-chlor (NaCl) particle, Repone K (KCl) particle, calcium chloride (CaCl
2) in particle, paraffin particles, sucrose granules, sodium hydroxide (NaOH) particle etc. one or more.
10. like any described preparation method in the claim 1～6, it is characterized in that,
Said organic solvent can be silicone oil, ethanol etc.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601911A (en) * | 2013-11-22 | 2014-02-26 | 中国工程物理研究院化工材料研究所 | Silicone rubber microporous material and preparation method thereof |
| CN105169478A (en) * | 2015-09-11 | 2015-12-23 | 深圳爱生再生医学科技有限公司 | 3D composite cytoskeleton and preparation method thereof |
| CN105585767A (en) * | 2015-08-27 | 2016-05-18 | 浙江瑞堂塑料科技有限公司 | Porous rotationally-molded product and preparation method thereof |
| CN106660889A (en) * | 2014-04-24 | 2017-05-10 | 奥斯设计公司 | Methods of forming a porous ceramic shaped article and porous ceramic products |
| CN107286639A (en) * | 2017-07-05 | 2017-10-24 | 佛山杰致信息科技有限公司 | Environment-protecting thermoplastic high polymer material and preparation method thereof |
| CN107876775A (en) * | 2017-10-27 | 2018-04-06 | 兰州理工大学 | A kind of porous Ti of structure-controllable low damage processing method |
| CN108473714A (en) * | 2015-10-09 | 2018-08-31 | 惠普发展公司，有限责任合伙企业 | Particle mixture |
| CN109020701A (en) * | 2018-09-11 | 2018-12-18 | 浙江世佳科技有限公司 | A kind of high-performance bio bacterial manure |
| CN112028620A (en) * | 2020-08-06 | 2020-12-04 | 同济大学 | Porous hydroxyapatite bioactive material and preparation method and application thereof |
| CN113164654A (en) * | 2018-11-15 | 2021-07-23 | 克莱蒙奥弗涅大学 | Implants with controlled porosity made of hybrid materials doped with osteoinductive nutrients |
| CN113368307A (en) * | 2021-01-04 | 2021-09-10 | 山东百多安医疗器械股份有限公司 | Ear support construction material and preparation process thereof |
| CN115926242A (en) * | 2023-02-01 | 2023-04-07 | 绿健体育产业科技(山西)有限公司 | Preparation method of water-permeable inorganic/organic plastic track composite material |
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| CN1493615A (en) * | 2003-06-20 | 2004-05-05 | 四川大学 | Inorganic/organic nano-composite bioactivity porous material and its preparation method |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601911A (en) * | 2013-11-22 | 2014-02-26 | 中国工程物理研究院化工材料研究所 | Silicone rubber microporous material and preparation method thereof |
| CN106660889A (en) * | 2014-04-24 | 2017-05-10 | 奥斯设计公司 | Methods of forming a porous ceramic shaped article and porous ceramic products |
| CN106660889B (en) * | 2014-04-24 | 2020-05-15 | 奥斯设计公司 | Method for forming porous ceramic shaped article and porous ceramic product |
| CN105585767A (en) * | 2015-08-27 | 2016-05-18 | 浙江瑞堂塑料科技有限公司 | Porous rotationally-molded product and preparation method thereof |
| CN105169478A (en) * | 2015-09-11 | 2015-12-23 | 深圳爱生再生医学科技有限公司 | 3D composite cytoskeleton and preparation method thereof |
| CN108473714A (en) * | 2015-10-09 | 2018-08-31 | 惠普发展公司，有限责任合伙企业 | Particle mixture |
| CN107286639A (en) * | 2017-07-05 | 2017-10-24 | 佛山杰致信息科技有限公司 | Environment-protecting thermoplastic high polymer material and preparation method thereof |
| CN107876775B (en) * | 2017-10-27 | 2019-11-12 | 兰州理工大学 | A kind of low damage processing method of the porous Ti of structure-controllable |
| CN107876775A (en) * | 2017-10-27 | 2018-04-06 | 兰州理工大学 | A kind of porous Ti of structure-controllable low damage processing method |
| CN109020701A (en) * | 2018-09-11 | 2018-12-18 | 浙江世佳科技有限公司 | A kind of high-performance bio bacterial manure |
| CN113164654A (en) * | 2018-11-15 | 2021-07-23 | 克莱蒙奥弗涅大学 | Implants with controlled porosity made of hybrid materials doped with osteoinductive nutrients |
| CN112028620A (en) * | 2020-08-06 | 2020-12-04 | 同济大学 | Porous hydroxyapatite bioactive material and preparation method and application thereof |
| CN112028620B (en) * | 2020-08-06 | 2021-10-08 | 同济大学 | Porous hydroxyapatite bioactive material and preparation method and application thereof |
| CN113368307A (en) * | 2021-01-04 | 2021-09-10 | 山东百多安医疗器械股份有限公司 | Ear support construction material and preparation process thereof |
| CN113368307B (en) * | 2021-01-04 | 2023-02-10 | 山东百多安医疗器械股份有限公司 | Ear support construction material and preparation process thereof |
| CN115926242A (en) * | 2023-02-01 | 2023-04-07 | 绿健体育产业科技(山西)有限公司 | Preparation method of water-permeable inorganic/organic plastic track composite material |
| CN115926242B (en) * | 2023-02-01 | 2024-02-23 | 绿健体育科技(山西)股份有限公司 | Preparation method of water-permeable inorganic/organic plastic track composite material |
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Application publication date: 20120725 |