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CN103656753A - Neutral calcium phosphate bone cement and preparation method thereof - Google Patents

Neutral calcium phosphate bone cement and preparation method thereof Download PDF

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Publication number
CN103656753A
CN103656753A CN201310642406.5A CN201310642406A CN103656753A CN 103656753 A CN103656753 A CN 103656753A CN 201310642406 A CN201310642406 A CN 201310642406A CN 103656753 A CN103656753 A CN 103656753A
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bone cement
preparation
neutral
calcium phosphate
series
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CN201310642406.5A
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CN103656753B (en
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刘涛
杨迪诚
何丹农
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Abstract

The invention relates to a method belonging to the technical field of biomedical materials, and concretely relates to a neutral calcium phosphate bone cement and a preparation method thereof. The preparation method is characterized in that the preparation method comprises the following steps: preparing a bone cement powder main component by appropriately controlling reaction conditions; adding a certain amount of hydroxyapatite and silicate to the above powder, and fully and uniformly mixing to prepare bone cement powder; and blending the bone cement powder with a citric acid-containing solidification liquid according to a certain liquid/solid ratio to obtain neutral bone cement, and putting solidified bone cement in water to obtain a neutral solution. The preparation method of the neutral bone cement enriches the range of the bone cement powder, allows acidic solidification liquids to be widely applied in injectable bone cements, and has the advantages of simplicity, feasibility, good effect, suitableness for the popularization in different acidic solidification liquids, and large scale application.

Description

Neutral bone cement of series of calcium phosphate and preparation method thereof
Technical field
The present invention relates to a kind of method of bio-medical material technical field, specifically a kind of neutral calcium phosphate pastern bone cement and preparation method thereof.
Background technology
In some calcium phosphate bone cement systems, in order to promote better bone cement powder curing molding and to keep high compressive strength, generally need in bone cement consolidation liquid, add a large amount of citric acid [ M. Anirban Jyoti, Applied Surface Science, 2010 ].Blemish in an otherwise perfect thing, citric acid, when effectively promoting bone cement curing molding and keeping advantages of higher compressive strength, also often causes bone cement to be highly acid.The existence of a large amount of protons generally can cause cell death, has seriously limited its application in vivo.
The present invention is directed to above background with not enough, bone cement of a kind of novelty and preparation method thereof is provided, by preparation technology and the composition of regulation and control bone cement, when improving bone cement mechanical strength, the highly acid problem that can effectively avoid traditional method to bring.
Summary of the invention
The object of the present invention is to provide neutral bone cement of a kind of novelty and preparation method thereof, preparation technology and one-tenth thereof by regulation and control bone cement are grouped into, when improving bone cement mechanical strength, can effectively avoid the highly acid problem of the bone cement that traditional method brings.
Object of the present invention is achieved through the following technical solutions: a certain proportion of calcium hydrogen phosphate is fully mixed with calcium carbonate powder; Then adopt the method for solid state reaction, by controlling rightly reaction condition, prepare bone cement powder main body composition.On this basis toward adding a certain amount of hydroxyapatite in powder and the abundant mix homogeneously of silicate is prepared bone cement powder.Bone cement powder and the consolidation liquid that contains citric acid are in harmonious proportion by certain liquid-solid ratio, can obtain hardening time without significant prolongation or the neutral bone cement that shortens to some extent.
A preparation method for the neutral bone cement of series of calcium phosphate, is characterized in that, comprises the following steps:
(1) will after calcination in 900 ℃ of stoves after raw material mixing, ball milling, obtain bone cement powder main body composition;
(2) toward adding hydroxyapatite in bone cement powder main body composition and silicate is prepared bone cement powder;
(3) if bone cement powder for a long time need not, be stored in 4 ℃ of dry enclosed environments;
(4) bone cement powder and acid consolidation liquid are in harmonious proportion by liquid-solid ratio, can obtain the neutral bone cement of series of calcium phosphate.
The described raw material of step (1) is that mol ratio is that 2:0.90 is to calcium hydrogen phosphate and the calcium carbonate mixture of 2:1.15.
The described hydroxyapatite of step (2) is of a size of and is less than 5 mm, and its content in bone cement powder is 0.05-60%.
The described silicate of step (2) is a kind of or its combination in sodium silicate, potassium silicate, calcium silicates, and its content in bone cement is 0-30%.
The described dry enclosed environment of step (3) is that outside air can not directly contact with bone cement powder.
The described dry enclosed environment of step (3) is for to be placed in bone cement powder the inert gas environments such as nitrogen, argon, or after evacuation, is placed in exsiccator, electronic dry cabinet.
The described acid consolidation liquid of step (4) is that citric acid content is at the solution of 3-55%, or take it as basis interpolation 0.01-5% hydroxypropyl emthylcellulose, the sodium carboxymethyl cellulose of 0.01-2%, 0.01-4% chitosan, 0.01-2% gelatin, 0.01-1.5% polyvinyl alcohol, 0.01-10% Polyethylene Glycol, 0.01-2% sodium alginate, 0.01-5% starch, 0.01-1% hyaluronic acid, 0.01-2% collagen protein, 0.5-40% glycerol, 0.01-15% sodium sulfate, 0.01-15% potassium sulfate, 0.01-15% ammonium sulfate, 0.01-10% magnesium sulfate, 0.01-10% sodium chloride, 0.01-10% potassium chloride, 0.01-15% calcium chloride, 0.01-15% sodium glycerophosphate, 0.01-15% glucose, 0.01-15% mannose, a kind of or its combination wherein of 0.01-5% cyclodextrin.
The described liquid-solid ratio of step (4) is to add 0.30-0.70 milliliter consolidation liquid in every 1 gram of bone cement powder.
The neutral bone cement of series of calcium phosphate preparing according to method described in above-mentioned any one, its pH value is 5-9, after solidifying, apparent density is not less than 1.30 g/cm 3, defeated and dispersed coefficient is not more than 5%.
The present invention is grouped into and is prepared a kind of Bone Colonizable Cements In Rabbits powder by the regulation and control preparation technology of bone cement and one-tenth thereof.Gained bone cement powder can be consolidation liquid curing molding with citric acid effectively, keeps higher mechanical strength simultaneously.Preparation method provided by the invention is simple, easily capable, effective, be suitable for containing in the consolidation liquid system of citric acid and promoting the use of in difference, can large-scale application.
Apparent density method of testing is: first adopt the cylindrical mold of diameter 6 mm height 10 mm to prepare bone cement sample, then measure actual diameter, height and the quality of solidifying the bone cement sample after 24 hours, calculate its density and be apparent density.
The method of testing of defeated and dispersed coefficient is: after solidifying, bone cement soaks after 10 days quality and reduces percentage ratio as defeated and dispersed coefficient in water.
PH value method of testing containing bone cement aqueous solution is: the bone cement that 1.0 g were solidified after 24 hours is placed in 20 mL ultra-pure waters, then with pH meter, measures it at the pH value of different soak times.
Accompanying drawing explanation
Figure 1 shows that solidifying rear bone cement is placed on rear pH temporal evolution curve in water.
The specific embodiment
Following examples be take invention technical scheme and are implemented as prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention are not limited to following embodiment.
Embodiment 1:
Take 86 g calcium phosphate dibasic dihydrates and 25 g calcium carbonate, joined ball milling mix homogeneously in 165 mL water.Then by water distilling under reduced pressure, in 80 ℃ of vacuum drying ovens, be dried and obtain mixed powder.After burning 15 hours, 900 ℃ of stove stage casings adopt wet ball grinding to obtain bone cement dispersion liquid powder body.After dispersion liquid is centrifugal, dry, obtain bone cement powder main body composition, powder body is of a size of 300-800 nm.
Embodiment 2:
96 g bone cement powder main body compositions and 4 g hydroxyapatite are ground and evenly obtain bone cement powder with mortar.Consolidation liquid and bone cement powder that 20% citric acid-1% hydroxypropyl emthylcellulose is formed are in harmonious proportion by the liquid-solid ratio of 0.5 mL/g, and it is 11 min that reference standard ASTM C191 measures the presetting period.After solidifying, bone cement apparent density is 1.45 g/cm 3, defeated and dispersed coefficient is 1.5%.Be added to the water, it is neutral that solution is.After standing one week, test solution pH is substantially constant, and as shown in Figure 1, aqueous solution pH keeps neutral at long period yardstick always.
Embodiment 3:
91 g bone cement powder main body compositions and 4 g hydroxyapatite and 5 g sodium silicate are ground and evenly obtain bone cement powder with mortar.Consolidation liquid and bone cement powder that 20% citric acid-1% hydroxypropyl emthylcellulose is formed are in harmonious proportion by the liquid-solid ratio of 0.5 mL/g, and it is 9 min that reference standard ASTM C191 measures the presetting period.After solidifying, bone cement apparent density is 1.48 g/cm 3, defeated and dispersed coefficient 2.2%.Be added to the water, it is neutral that solution is.After standing one week, pH value of solution is substantially constant, similar shown in result and Fig. 1.

Claims (9)

1. a preparation method for the neutral bone cement of series of calcium phosphate, is characterized in that, comprises the following steps:
(1) will after calcination in 900 ℃ of stoves after raw material mixing, ball milling, obtain bone cement powder main body composition;
(2) toward adding hydroxyapatite in bone cement powder main body composition and silicate is prepared bone cement powder;
(3) if bone cement powder for a long time need not, be stored in 4 ℃ of dry enclosed environments;
(4) bone cement powder and acid consolidation liquid are in harmonious proportion by liquid-solid ratio, can obtain the neutral bone cement of series of calcium phosphate.
2. the preparation method of the neutral bone cement of series of calcium phosphate according to claim 1, is characterized in that, the described raw material of step (1) is that mol ratio is that 2:0.90 is to calcium hydrogen phosphate and the calcium carbonate mixture of 2:1.15.
3. the preparation method of the neutral bone cement of series of calcium phosphate according to claim 1, is characterized in that, the described hydroxyapatite of step (2) is of a size of and is less than 5 mm, and its content in bone cement powder is 0.05-60%.
4. the preparation method of the neutral bone cement of series of calcium phosphate according to claim 1, is characterized in that, the described silicate of step (2) is a kind of or its combination in sodium silicate, potassium silicate, calcium silicates, and its content in bone cement is 0-30%.
5. the preparation method of the neutral bone cement of series of calcium phosphate according to claim 1, is characterized in that, the described dry enclosed environment of step (3) is that outside air can not directly contact with bone cement powder.
6. the preparation method of the neutral bone cement of series of calcium phosphate according to claim 5, it is characterized in that, the described dry enclosed environment of step (3) is for to be placed in bone cement powder the inert gas environments such as nitrogen, argon, or after evacuation, is placed in exsiccator, electronic dry cabinet.
7. the preparation method of the neutral bone cement of series of calcium phosphate according to claim 1, it is characterized in that, the described acid consolidation liquid of step (4) is that citric acid content is at the solution of 3-55%, or take it as basis interpolation 0.01-5% hydroxypropyl emthylcellulose, the sodium carboxymethyl cellulose of 0.01-2%, 0.01-4% chitosan, 0.01-2% gelatin, 0.01-1.5% polyvinyl alcohol, 0.01-10% Polyethylene Glycol, 0.01-2% sodium alginate, 0.01-5% starch, 0.01-1% hyaluronic acid, 0.01-2% collagen protein, 0.5-40% glycerol, 0.01-15% sodium sulfate, 0.01-15% potassium sulfate, 0.01-15% ammonium sulfate, 0.01-10% magnesium sulfate, 0.01-10% sodium chloride, 0.01-10% potassium chloride, 0.01-15% calcium chloride, 0.01-15% sodium glycerophosphate, 0.01-15% glucose, 0.01-15% mannose, a kind of or its combination wherein of 0.01-5% cyclodextrin.
8. the preparation method of the neutral bone cement of series of calcium phosphate according to claim 1, is characterized in that, the described liquid-solid ratio of step (4) is to add 0.30-0.70 milliliter consolidation liquid in every 1 gram of bone cement powder.
9. the neutral bone cement of series of calcium phosphate preparing according to method described in claim 1-8 any one, its pH value is 5-9, after solidifying, apparent density is not less than 1.30 g/cm 3, defeated and dispersed coefficient is not more than 5%.
CN201310642406.5A 2013-12-04 2013-12-04 Neutral calcium phosphate bone cement and preparation method thereof Expired - Fee Related CN103656753B (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104524627A (en) * 2014-12-23 2015-04-22 南京航空航天大学 Method for preparing high-strength novel hydroxyapatite bone cement
CN106267365A (en) * 2016-08-17 2017-01-04 林春梅 A kind of enhancing activity injecting bone cement and preparation method thereof
CN106540317A (en) * 2016-12-08 2017-03-29 苏州艾博迈尔新材料有限公司 A kind of realizing controlled-release bone cement and preparation method thereof
CN106620886A (en) * 2016-12-09 2017-05-10 苏州纳贝通环境科技有限公司 Liquid bracket material for bone repair and preparation method 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
CN108273131A (en) * 2018-03-19 2018-07-13 深圳市中科海世御生物科技有限公司 A kind of composite bone cement, preparation method and applications and a kind of bone renovating material
CN109498846A (en) * 2018-10-09 2019-03-22 广州润虹医药科技股份有限公司 Bone repairing support and preparation method thereof that is a kind of while discharging zinc ion and strontium ion
CN110201228A (en) * 2019-04-19 2019-09-06 湖北联结生物材料有限公司 A kind of calcium phosphate bone cement and its preparation method and application containing decalcified bone matrix

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104524627A (en) * 2014-12-23 2015-04-22 南京航空航天大学 Method for preparing high-strength novel hydroxyapatite bone cement
CN106267365A (en) * 2016-08-17 2017-01-04 林春梅 A kind of enhancing activity injecting bone cement and preparation method 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
CN106540317A (en) * 2016-12-08 2017-03-29 苏州艾博迈尔新材料有限公司 A kind of realizing controlled-release bone cement and preparation method thereof
CN106620886A (en) * 2016-12-09 2017-05-10 苏州纳贝通环境科技有限公司 Liquid bracket material for bone repair and preparation method thereof
CN108273131A (en) * 2018-03-19 2018-07-13 深圳市中科海世御生物科技有限公司 A kind of composite bone cement, preparation method and applications and a kind of bone renovating material
CN109498846A (en) * 2018-10-09 2019-03-22 广州润虹医药科技股份有限公司 Bone repairing support and preparation method thereof that is a kind of while discharging zinc ion and strontium ion
CN109498846B (en) * 2018-10-09 2021-07-16 广州润虹医药科技股份有限公司 Bone repair scaffold capable of releasing zinc ions and strontium ions simultaneously and preparation method thereof
CN110201228A (en) * 2019-04-19 2019-09-06 湖北联结生物材料有限公司 A kind of calcium phosphate bone cement and its preparation method and application containing decalcified bone matrix

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