CN101125219A - Rapidly solidified calcium phosphate cement composite material and its preparation method - Google Patents
Rapidly solidified calcium phosphate cement composite material and its preparation method Download PDFInfo
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- CN101125219A CN101125219A CNA200710017126XA CN200710017126A CN101125219A CN 101125219 A CN101125219 A CN 101125219A CN A200710017126X A CNA200710017126X A CN A200710017126XA CN 200710017126 A CN200710017126 A CN 200710017126A CN 101125219 A CN101125219 A CN 101125219A
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- bone cement
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Abstract
The present invention discloses a quick-concreting composite material of calcium phosphate solid cement, comprising a solid phasing part and a liquid phasing part; the preparation method of the composite material is that: preparing Alpha-TCP solid cement powder with solid-state sintering; forcing the Alpha-TCP cement powder and the carbon nanotube via the ball mill, and then acquiring the solid cement composite powder; putting the different quantity of chitosan and Beta-sodium glycero-phosphate respectively into the dilute hydrochloric acid and deionized water, obtaining the mixing liquid of solid cement; putting the solid cement composite powder and the hydroxyapatite seed into the mixing liquid of solid cement; evenly mixing the solid cement slurry and then pouring into the mould to be exhausted and planned; acquiring quick-concreting composite material of calcium phosphate solid cement. The present invention provides a quick-concreting composite material of calcium phosphate solid cement which has great mechanical property, short concreting time, certain bioelectromagnetic effects and good biocompatibility, and the preparation method.
Description
One, technical field
The present invention relates to a kind of bone-cement composite material and preparation method thereof, relate in particular to a kind of rapidly solidified calcium phosphate cement composite material and preparation method thereof.Belong to material science and biomedical crossing domain.
Two, background technology
Calcium phosphate bone cement (CPC) is a kind of novel type bioactive bone cement admittedly certainly, has excellent biological compatibility, bone conductibility, degradability, plasticity, and the heat that reaction produces is few, be ideal bone replacement and repair materials but the calcium phosphate bone cement setting rate is slow, low, the poor mechanical property of intensity, mechanical property is only between spongy bone and cortical bone, and the ability of the big and bearing load of fragility has limited its application greatly.Because hollow tubular structure and performance and the potential application in nano electron device and high-performance nano material thereof that CNT (CNTs) is unique, it is once finding to have received concern widely at once.That CNT has is very unique, very perfect microstructure and very large length through than, have extraordinary mechanical property and good electric property simultaneously, the ideal that is considered to nano composite material is added phase.Chitosan-sodium glycerophosphate thermosensitive hydrogel system is the novel drug-supplying system that just is suggested recent years, have under the preservation condition and exist with solution state, but take place immediately to change mutually because of the agents area temperature reaches 37 ℃ after the administration, form the characteristic of semi-solid gel.
Three, summary of the invention
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art, provide a kind of mechanical property superior, setting time is short, and has certain bioelectromagnetics effect and rapidly solidified calcium phosphate cement composite material of good biocompatibility and preparation method thereof.
The present invention realizes in the following manner:
A kind of rapidly solidified calcium phosphate cement composite material of the present invention, comprise solid phase and liquid phase two parts, the percentage by weight that it is characterized in that each constituent content of solid phase part is: CNT 0.1%-1%, hydroxyapatite 1%-10%, type alpha tricalcium phosphate type bone cement powder body 89.9%-98.9%; Liquid phase part is the distiller liquor that chitosan/sodium is formed; The ratio of liquid phase and solid phase is: 0.2-1ml/g.
Wherein type alpha tricalcium phosphate type bone cement and chitosan/sodium distiller liquor is made by following step:
With analytically pure dicalcium phosphate dehydrate (DCPD) oven dry 10h under 120 ℃, with analytically pure CaCO
3Powder adopts dry ball milling to mix by 2: 1 mol ratio (mol), mixed powder is fired to 1250 ℃ in high temperature sintering furnace, take out rapidly behind the insulation 2h, reduce to room temperature, obtain white loose shape type alpha tricalcium phosphate type bone cement powder body with 100 ℃ of-150 ℃/min speed chillings;
With deacetylation is that 95% chitosan is dissolved in 0.1molL
-1In the hydrochloric acid, fully stir, be mixed with the settled solution of 15-25mg/ml chitosan; With deionized water sodium is mixed with the solution of 0.6-1.0g/ml,, be 1: 9 mixed with sodium solution and chitosan solution according to volume ratio then, mix the back and continue to stir 10-30 minute, make the distiller liquor of bone cement.
The preparation method of a kind of rapidly solidified calcium phosphate cement composite material of the present invention, realized by following steps:
1) with analytically pure dicalcium phosphate dehydrate (DCPD) oven dry 8-10h under 120 ℃, with analytically pure CaCO
3Powder adopts dry ball milling to mix by 2: 1 mol ratio (mol), mixed powder is fired to 1250 ℃ in high temperature sintering furnace, take out rapidly behind the insulation 2h, reduce to room temperature, obtain white loose shape type alpha tricalcium phosphate type bone cement powder body with 100 ℃ of-150 ℃/min speed chillings;
2) in weight ratio, type alpha tricalcium phosphate type bone cement powder body and CNT are pressed 89.9-98.9: the 0.1-1 mixed is narrower than 200 orders by mechanical ball milling and obtains the bone cement composite granule;
3) be that 95% chitosan is dissolved in 0.1molL with deacetylation
-1In the hydrochloric acid, fully stir, be mixed with the settled solution of 15-25mg/ml chitosan; With deionized water sodium being mixed with the solution of 0.6-1.0g/ml, is 1: 9 mixed with sodium solution and chitosan solution according to volume ratio then, mixes the back and continues to stir 10-30 minute, makes the distiller liquor of bone cement;
4) in weight ratio, with the bone cement composite granule of step 2 gained and hydroxyapatite crystal seed in 90-99: 1-10 ratio uniform mixing, liquid-solid ratio according to 0.2-1ml/g adds the prepared bone cement distiller liquor of step 3, and the firm time of regulating bone cement was at 4-10 minute;
5) the bone cement slurry with step 4 gained mixes, and it is flat to pour in the mould aerofluxus shake into;
6) sample being placed temperature is 37 ℃, and humidity is in 100% the calorstat, to be incubated 20-30 hour, can get corresponding rapidly solidified calcium phosphate cement Biocomposite material.
The rapidly solidified calcium phosphate cement composite material of the present invention's preparation owing to adopt the distiller liquor of the thermosensitive hydrogel system of chitosan/sodium composition as bone cement, has shortened the setting time of calcium phosphate bone cement.Because the adding of CNT and chitosan makes composite have higher mechanical property, certain bioelectromagnetics effect and excellent biological compatibility are arranged simultaneously.This calcium phosphate cement composite material can be used for the damaged filling of bone, repaiies, and can be used for the transplanting and the replacement of non-bearing bone that the material combination property is had relatively high expectations.
Four, the specific embodiment
Embodiment 1
1) analytically pure dicalcium phosphate dehydrate (DCPD) oven dry 10h under 120 ℃ is with analytically pure CaCO
3Powder adopts dry ball milling to mix 200 mesh sieves by 2: 1 mol ratio (mol), mixed powder is fired to 1250 ℃ in high temperature sintering furnace, take out rapidly behind the insulation 2h, reduce to room temperature, obtain the white loose shape type alpha tricalcium phosphate type bone cement (powder body of α-TCP) with 120 ℃/min speed chilling;
2) in the amount of percentage by weight, 99.4% type alpha tricalcium phosphate type bone cement and 0.6% CNT are obtained the bone cement composite granule by mechanical ball milling;
3) be that 95% chitosan is dissolved in 4.5ml 0.1molL with the 100mg deacetylation
-1In the hydrochloric acid, fully stirred 2 hours, get settled solution; The 500mg sodium is dissolved in the 0.5ml deionized water, is that 1: 9 ratio drops in the chitosan solution according to volume ratio, just drips the limit and stirs, and solution mixes the back to be continued to stir 20 minutes, makes the distiller liquor of bone cement;
4) in the amount of percentage by weight, 95% bone cement composite granule and 5% hydroxyapatite crystal seed are added the prepared bone cement distiller liquor of step 3, addition is regulated the firm time of bone cement according to the ratio of every gram 0.4ml;
5) with the bone cement slurry mix homogeneously of step 4 gained, it is flat to pour in the mould aerofluxus shake into, makes smooth sample;
6) sample being placed temperature is 37 ℃, and humidity is in the 100% so-called calorstat, is incubated 20-30 hour, can get corresponding rapidly solidified calcium phosphate cement Biocomposite material.
After measured, make the main performance of CNT-chitosan-tricalcium phosphate bone cement: presetting period 5min, final setting time 25min, bending strength 13.31Mpa,, biocompatibility is better.
Embodiment 2
1) analytically pure dicalcium phosphate dehydrate (DCPD) oven dry 10h under 120 ℃ is with analytically pure CaCO
3Powder is used in method ball milling mixing mixed powder by 2: 1 (mol) and is fired to 1250 ℃ in high temperature sintering furnace, takes out rapidly behind the insulation 2h, reduces to room temperature with 120 ℃/min speed chilling, obtains the white loose shape type alpha tricalcium phosphate type bone cement (powder body of α-TCP);
2) in the amount of percentage by weight, 99.5% type alpha tricalcium phosphate type bone cement and 0.5% CNT are obtained the bone cement composite granule by mechanical ball milling;
3) be that 95% chitosan is dissolved in 4.5ml 0.1molL with the 90mg deacetylation
-1In the hydrochloric acid, fully stirred 2 hours, get settled solution; The 400mg sodium is dissolved in the 0.5ml deionized water, is that 1: 9 ratio drops in the chitosan solution according to volume ratio, just drips the limit and stirs, and solution mixes the back to be continued to stir 20 minutes, makes the distiller liquor of bone cement;
4) in the amount of percentage by weight, 95% bone cement composite granule and 5% hydroxyapatite crystal seed are added the prepared bone cement distiller liquor of step 3, addition is regulated the firm time of bone cement according to the ratio of every gram 0.5ml;
5) with the bone cement slurry mix homogeneously of step 4 gained, it is flat to pour in the mould aerofluxus shake into, makes smooth sample;
6) sample being placed temperature is 37 ℃, and humidity is in 100% the calorstat, to be incubated 20-30 hour, can get corresponding rapidly solidified calcium phosphate cement Biocomposite material.
After measured, make the main performance of CNT-chitosan-tricalcium phosphate bone cement: presetting period 7min, final setting time 30min bending strength 12.99Mpa,, biocompatibility is better.
Claims (2)
1. rapidly solidified calcium phosphate cement composite material, comprise solid phase and liquid phase two parts, the percentage by weight that it is characterized in that each constituent content of solid phase part is: CNT 0.1%-1%, hydroxyapatite 1%-10%, type alpha tricalcium phosphate type bone cement powder body 89.9%-98.9%; Liquid phase part is the distiller liquor that chitosan/sodium is formed; The ratio of liquid phase and solid phase is: 0.2-1ml/g;
Wherein type alpha tricalcium phosphate type bone cement and chitosan/sodium distiller liquor is made by following step:
With analytically pure dicalcium phosphate dehydrate (DCPD) oven dry 10h under 120 ℃, with analytically pure CaCO
3Powder adopts dry ball milling to mix by 2: 1 mol ratio (mol), mixed powder is fired to 1250 ℃ in high temperature sintering furnace, take out rapidly behind the insulation 2h, reduce to room temperature, obtain white loose shape type alpha tricalcium phosphate type bone cement powder body with 100 ℃ of-150 ℃/min speed chillings;
With deacetylation is that 95% chitosan is dissolved in 0.1molL
-1In the hydrochloric acid, fully stir, be mixed with the settled solution of 15-25mg/ml chitosan; With deionized water sodium is mixed with the solution of 0.6-1.0g/ml,, be 1: 9 mixed with sodium solution and chitosan solution according to volume ratio then, mix the back and continue to stir 10-30 minute, make the distiller liquor of bone cement.
2. the preparation method of the described a kind of rapidly solidified calcium phosphate cement composite material of claim 1, realized by following steps:
1) with analytically pure dicalcium phosphate dehydrate (DCPD) oven dry 8-10h under 120 ℃, with analytically pure CaCO
3Powder adopts dry ball milling to mix by 2: 1 mol ratio (mol), mixed powder is fired to 1250 ℃ in high temperature sintering furnace, take out rapidly behind the insulation 2h, reduce to room temperature, obtain white loose shape type alpha tricalcium phosphate type bone cement powder body with 100 ℃ of-150 ℃/min speed chillings;
2) in weight ratio, type alpha tricalcium phosphate type bone cement powder body and CNT are pressed 89.9-98.9: the 0.1-1 mixed is narrower than 200 orders by mechanical ball milling and obtains the bone cement composite granule;
3) be that 95% chitosan is dissolved in 0.1molL with deacetylation
-1In the hydrochloric acid, fully stir, be mixed with the settled solution of 15-25mg/ml chitosan; With deionized water sodium being mixed with the solution of 0.6-1.0g/ml, is 1: 9 mixed with sodium solution and chitosan solution according to volume ratio then, mixes the back and continues to stir 10-30 minute, makes the distiller liquor of bone cement;
4) in weight ratio, with the bone cement composite granule of step 2 gained and hydroxyapatite crystal seed in 90-99: 1-10 ratio uniform mixing, liquid-solid ratio according to 0.2-1ml/g adds the prepared bone cement distiller liquor of step 3, and the firm time of regulating bone cement was at 4-10 minute;
5) the bone cement slurry with step 4 gained mixes, and it is flat to pour in the mould aerofluxus shake into;
6) sample being placed temperature is 37 ℃, and humidity is in 100% the calorstat, to be incubated 20-30 hour, can get corresponding rapidly solidified calcium phosphate cement Biocomposite material.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011139136A1 (en) * | 2010-05-06 | 2011-11-10 | Universiti Sains Malaysia | Calcium phosphate cement composition and method of making the same |
| CN102526798A (en) * | 2012-01-18 | 2012-07-04 | 华东理工大学 | Injectable compound bone cement and preparation method thereof |
| CN102557527A (en) * | 2012-01-04 | 2012-07-11 | 河南科技大学 | Temperature control magnetic bone cement and preparation method thereof |
| CN102813962A (en) * | 2012-07-12 | 2012-12-12 | 同济大学 | Injectable and degradable bone cement, and preparation method and application thereof |
| CN102026933B (en) * | 2008-05-29 | 2013-10-30 | Sika技术股份公司 | Additive for hydraulic binding agent with long processing time and high early strength |
| CN102131744B (en) * | 2008-04-30 | 2016-10-05 | 米纳斯吉拉斯联合大学 | The method of synthesizing carbon nanotubes continuous, extensive and nanostructured products on clinker |
| CN106581749A (en) * | 2016-12-20 | 2017-04-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Thermo-sensitive PEG (polyethylene glycol) polyester block copolymer modified injectable calcium phosphate bone cement and preparation method and application thereof |
| CN106729971A (en) * | 2016-11-23 | 2017-05-31 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of modified calcium phosphate bone cement of water-soluble mono wall carbon nano tube and preparation and application |
| CN106892609A (en) * | 2017-03-27 | 2017-06-27 | 四川大学 | The preparation method and purposes of the organic-inorganic spontaneous coagulation composite of a kind of new glycerophosphate and calcium silicates salt |
| CN107362389A (en) * | 2017-06-16 | 2017-11-21 | 山东大学 | A kind of calcium phosphate biological bone cement composite of CNT and graphene enhancing |
| CN107473697A (en) * | 2017-07-25 | 2017-12-15 | 成都理工大学 | Earthen ruins Dam Foundation Strengthened in Situ repair materials, its preparation method and application |
| CN107773784A (en) * | 2017-10-30 | 2018-03-09 | 西南交通大学 | A kind of magnetic bone cement and preparation method thereof |
| CN111012946A (en) * | 2019-12-31 | 2020-04-17 | 广州润虹医药科技股份有限公司 | Thermo-sensitive calcium phosphate bone cement and preparation method thereof |
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2007
- 2007-09-04 CN CNA200710017126XA patent/CN101125219A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102131744B (en) * | 2008-04-30 | 2016-10-05 | 米纳斯吉拉斯联合大学 | The method of synthesizing carbon nanotubes continuous, extensive and nanostructured products on clinker |
| CN102026933B (en) * | 2008-05-29 | 2013-10-30 | Sika技术股份公司 | Additive for hydraulic binding agent with long processing time and high early strength |
| WO2011139136A1 (en) * | 2010-05-06 | 2011-11-10 | Universiti Sains Malaysia | Calcium phosphate cement composition and method of making the same |
| CN102557527A (en) * | 2012-01-04 | 2012-07-11 | 河南科技大学 | Temperature control magnetic bone cement and preparation method thereof |
| CN102526798A (en) * | 2012-01-18 | 2012-07-04 | 华东理工大学 | Injectable compound bone cement and preparation method thereof |
| CN102813962A (en) * | 2012-07-12 | 2012-12-12 | 同济大学 | Injectable and degradable bone cement, and preparation method and application thereof |
| CN102813962B (en) * | 2012-07-12 | 2014-08-13 | 同济大学 | Injectable and degradable bone cement, and preparation method and application thereof |
| CN106729971A (en) * | 2016-11-23 | 2017-05-31 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of modified calcium phosphate bone cement of water-soluble mono wall carbon nano tube and preparation and application |
| CN106581749A (en) * | 2016-12-20 | 2017-04-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Thermo-sensitive PEG (polyethylene glycol) polyester block copolymer modified injectable calcium phosphate bone cement and preparation method and application thereof |
| CN106892609A (en) * | 2017-03-27 | 2017-06-27 | 四川大学 | The preparation method and purposes of the organic-inorganic spontaneous coagulation composite of a kind of new glycerophosphate and calcium silicates salt |
| CN106892609B (en) * | 2017-03-27 | 2019-12-06 | 四川大学 | Preparation method and application of glycerophosphate and calcium silicate organic-inorganic self-solidifying composite material |
| CN107362389A (en) * | 2017-06-16 | 2017-11-21 | 山东大学 | A kind of calcium phosphate biological bone cement composite of CNT and graphene enhancing |
| CN107362389B (en) * | 2017-06-16 | 2020-01-10 | 山东大学 | Carbon nanotube and graphene reinforced calcium phosphate biological bone cement composite material |
| CN107473697A (en) * | 2017-07-25 | 2017-12-15 | 成都理工大学 | Earthen ruins Dam Foundation Strengthened in Situ repair materials, its preparation method and application |
| CN107773784A (en) * | 2017-10-30 | 2018-03-09 | 西南交通大学 | A kind of magnetic bone cement and preparation method thereof |
| CN107773784B (en) * | 2017-10-30 | 2019-10-18 | 西南交通大学 | A kind of magnetism bone cement and preparation method thereof |
| CN111012946A (en) * | 2019-12-31 | 2020-04-17 | 广州润虹医药科技股份有限公司 | Thermo-sensitive calcium phosphate bone cement and preparation method thereof |
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