CN103656744B - Bone cement solidification liquid, and preparation method and application thereof - Google Patents
Bone cement solidification liquid, and preparation method and application thereof Download PDFInfo
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- CN103656744B CN103656744B CN201310642408.4A CN201310642408A CN103656744B CN 103656744 B CN103656744 B CN 103656744B CN 201310642408 A CN201310642408 A CN 201310642408A CN 103656744 B CN103656744 B CN 103656744B
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Abstract
The invention relates to a Bone cement solidification liquid, and a preparation method and an application thereof. The solidification liquid comprises, by mass, 3-55% of citric acid, 0.05-10% of phosphorylated chitosan, 15% or less of a water-soluble polymer, 20% or less of an inorganic salt, 45% or less of an organic micromolecule, and the balance water or an acid solution. The preparation method of the solidification liquid enriches a bone cement modification mode by using chitosan, has the advantages of simplicity, feasibility, and good effect, is suitable for the wide use in different inorganic calcium-based bone cement systems, and can be extensively used.
Description
Technical field
The present invention relates to a kind of method of biology medical material technical field, bone cement consolidation liquid formula of specifically a kind of phosphonized chitosan modification and preparation method thereof.
Background technology
Injectable calcium phosphate bone cement requires harsh to its combination property when being used for Bone Defect Repari, as good biocompatibility, bone conductibility, degradability, certain mechanical strength, anti-collapsibility, injectable etc.And calcium phosphate itself often can not meet above requirement simultaneously, generally modifier, reinforcing agent, cross-linking agent etc. must be added in series of calcium phosphate bone cement powder or consolidation liquid.
In numerous material, Chitosan-phospholipid complex is due to its good biocompatibility, degradable, have obvious potentiation to be subject to extensive concern to bone cement.Phosphonized chitosan is the common derivant of one in chitosan, and Chang Zuowei skeleton is replaced and drug controlled release material, is applicable to shaping and organizational project.In addition, phosphonized chitosan dissolubility and to the complexing power of metal ion comparatively chitosan itself have and significantly improve.Consider that series of calcium phosphate bone cement can relate to dissolving and the calcium phosphate recrystallize of calcium ion when solidifying.The introducing of phosphoric acid primitive can promote bone cement molding quickly and strengthen.If the respective advantages of chitosan and phosphate radical ought can be developed the more excellent Bone Colonizable Cements In Rabbits of combination property.
The present invention is directed to above background and the deficiencies in the prior art, a kind of Bone Colonizable Cements In Rabbits consolidation liquid and preparation method thereof is provided.
Summary of the invention
The object of the present invention is to provide a kind of Bone Colonizable Cements In Rabbits consolidation liquid formula and its preparation method and application.In conjunction with the advantage of traditional chitin modified bone cement and phosphate-modified bone cement, by synthetic route and formula preparation rightly, develop a kind of Bone Colonizable Cements In Rabbits consolidation liquid formula.
A kind of bone cement consolidation liquid, it is characterized in that, wherein each constituent mass percentage composition is as follows:
Citric acid: 3-55%;
Phosphonized chitosan: 0.05-10%;
Water soluble polymer class total amount is not more than 15%, wherein, sodium carboxymethyl cellulose: 0-5%, hyaluronic acid: 0-1%, hydroxypropyl emthylcellulose: 0-2%, polyvinyl alcohol: 0-1.5%, Polyethylene Glycol: 0-10%, starch: 0-5%, gelatin: 0-2%, collagen protein: 0-2%;
Inorganic salts total amount is not more than 20%, wherein, and sodium sulfate: 0-15%, potassium sulfate: 0-15%, ammonium sulfate: 0-15%, magnesium sulfate: 0-10%, sodium chloride: 0-10%, potassium chloride: 0-10%, calcium chloride: 0-15%;
Organic molecule class is not more than 45%, wherein, and sodium glycerophosphate: 0-15%, glucose: 0-15%, mannose: 0-15%, cyclodextrin: 0-5%, glycerol: 0-40%;
Surplus is water, or acid solution.
A preparation method for bone cement consolidation liquid, is characterized in that, comprises the following steps:
(1) preparation contains the solution of 3-55% citric acid and 0.05-10% phosphonized chitosan;
(2) a kind of or its combination added on the basis of citric acid-chitosan solution in water soluble polymer, inorganic salt or organic molecule modifier obtains final consolidation liquid;
(3) if consolidation liquid for a long time need not, be stored in 4 DEG C of environment, molten in advance before using;
(4) bone cement powder and consolidation liquid are in harmonious proportion by liquid-solid ratio, the bone cement of phosphonized chitosan modification can be obtained.
The solvent of the citrate-phosphate chitosan solution described in step (1) is aqueous solution, or acid solution.
Described acid solution is one in 0.01-0.3 M hydrochloric acid solution, 0.01-0.3 M sulfuric acid solution, 0.01-0.5 M phosphoric acid solution, 0.01-0.6 M acetic acid solution, 0.01-0.2 M salpeter solution, 0.01-0.5 M ascorbic acid solution, 0.01-0.5 M lactic acid solution or its combination.
The manner of formulation of the solution described in step (2) is room-temperature dissolution, or less than 60 DEG C are heated hydrotropy, can also be aided with mechanical agitation or magnetic agitation.
Pre-molten mode described in step (3) makes consolidation liquid become flowable liquid for heating below 37 DEG C.
The bone cement powder that bone cement powder described in step (5) is bata-tricalcium phosphate is main component, hydroxyapatite is auxiliary element, the content of hydroxyapatite is 0.5-49%.
Liquid-solid ratio described in step (5) is the consolidation liquid adding 0.30-0.70 milliliter in every 1 gram of bone cement powder.
A kind of bone cement consolidation liquid is as the application of bone cement consolidation liquid.
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 the actual diameter of the bone cement sample of solidification after 24 hours, height and quality, calculate its density and be apparent density.
The method of testing of defeated and dispersed coefficient is: after solidifying, bone cement to soak after 10 days Mass lost percentage ratio as defeated and dispersed coefficient in water.
PH value method of testing containing bone cement aqueous solution is: the bone cement after 1.0 g are solidified 24 hours is placed in 20 mL ultra-pure waters, then measures its pH value in different soak time with pH meter.
Intensity test method is: first adopt the cylindrical mold of diameter 6 mm height 10 mm to prepare bone cement sample, 37
oc, solidifies under 100% damp condition.Then omnipotent mechanics machine is utilized to measure the comprcssive strength of the bone cement sample of solidification after 24 hours.
Bone cement is when extruding injection without solid-liquid separation phenomenon, and injectability coefficient is not less than 80%, and the presetting period is no more than 40 min.Be added to the water pH value within the scope of 5-9 after its solidification, apparent density is not less than 1.30 g/cm
3, defeated and dispersed coefficient is not more than 3%, and comprcssive strength is not less than 2.5 MPa.
Detailed description of the invention
Following examples are implemented premised on invention technical scheme, give 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, 80
oin C vacuum drying oven, drying obtains mixed powder.By powder body 900
owet ball grinding is adopted to obtain bone cement dispersion liquid after 15 h are burnt in C stove stage casing.Obtain bone cement powder bulk composition after dispersion liquid is centrifugal, drying, be mainly bata-tricalcium phosphate.96 g bata-tricalcium phosphates and 4 g hydroxyapatite mix homogeneously are obtained bone cement powder.
Embodiment 2:
Take 0.2 g phosphonized chitosan to join in 10 mL 40 wt% aqueous citric acid solutions, the gross mass that adds water is 19.8 grams.Then add 0.2 gram of sodium carboxymethyl cellulose, obtain the consolidation liquid of phosphonized chitosan and sodium carboxymethyl cellulose modification.Be in harmonious proportion by the liquid-solid ratio of 0.5 mL/g by the bone cement powder be made up of bata-tricalcium phosphate and hydroxyapatite in consolidation liquid and embodiment 1, it is 31 min that reference standard ASTM C191 measures the presetting period.Injectability coefficient is 94%.Solidifying bone cement apparent density after 24 hours is 1.47 g/cm
3, in water, defeated and dispersed coefficient is 1.5%, comprcssive strength 6.7 MPa.Be added to the water, solution is in neutral.
Embodiment 3:
Take 0.2 g phosphonized chitosan to join in 10 mL 40 wt% aqueous citric acid solutions, the gross mass that adds water is 17.8 g.Then add 0.2 g sodium carboxymethyl cellulose and 2 g glycerol, obtain the consolidation liquid of phosphonized chitosan and sodium carboxymethyl cellulose modification.Be in harmonious proportion by the liquid-solid ratio of 0.5 mL/g by the bone cement powder be made up of bata-tricalcium phosphate and hydroxyapatite in consolidation liquid and embodiment 1, it is 23 min that reference standard ASTM C191 measures the presetting period.Injectability coefficient is 93%.Solidifying bone cement apparent density after 24 hours is 1.44 g/cm
3, in water, defeated and dispersed coefficient is 1.0%, comprcssive strength 7.0 MPa.Be added to the water, solution is in neutral.
Embodiment 4:
Take 0.2 g phosphonized chitosan to join in 10 mL 40 wt% aqueous citric acid solutions, the gross mass that adds water is 19.8 g.Then add 0.2 g gelatin, obtain phosphonized chitosan and gelatin modified consolidation liquid.Be in harmonious proportion by the liquid-solid ratio of 0.5 mL/g by the bone cement powder be made up of bata-tricalcium phosphate and hydroxyapatite in consolidation liquid and embodiment 1, it is 6 min that reference standard ASTM C191 measures the presetting period.Injectability coefficient is 97%.Solidifying bone cement apparent density after 24 hours is 1.45 g/cm
3, in water, defeated and dispersed coefficient is 0.9%, comprcssive strength 5.3 MPa.Be added to the water, solution is in neutral.
Embodiment 5:
Take 0.2 g phosphonized chitosan to join in 10 mL 40 wt% aqueous citric acid solutions, the gross mass that adds water is 17.8 g.Then add 0.2 g gelatin and 2 g glycerol, obtain phosphonized chitosan and gelatin modified consolidation liquid.Be in harmonious proportion by the liquid-solid ratio of 0.5 mL/g by the bone cement powder be made up of bata-tricalcium phosphate and hydroxyapatite in consolidation liquid and embodiment 1, it is 31 min that reference standard ASTM C191 measures the presetting period.Injectability coefficient is 94%.Solidifying bone cement apparent density after 24 hours is 1.46 g/cm
3, in water, defeated and dispersed coefficient is 1.3%, comprcssive strength 2.7 MPa.Be added to the water, solution is in neutral.
Embodiment 6:
Take 0.2 g phosphonized chitosan to join in 10 mL 40 wt% aqueous citric acid solutions, the gross mass that adds water is 19.8 g.Then add 0.2 g hydroxypropyl emthylcellulose, obtain the consolidation liquid of phosphonized chitosan and hydroxypropyl emthylcellulose modification.Be in harmonious proportion by the liquid-solid ratio of 0.5 mL/g by the bone cement powder be made up of bata-tricalcium phosphate and hydroxyapatite in consolidation liquid and embodiment 1, it is 19 min that reference standard ASTM C191 measures the presetting period.Injectability coefficient is 92%.Solidifying bone cement apparent density after 24 hours is 1.51 g/cm
3, in water, defeated and dispersed coefficient is 1.4%, comprcssive strength 4.6 MPa.Be added to the water, solution is in neutral.
Embodiment 7:
Take 0.2 g phosphonized chitosan to join in 10 mL 40 wt% aqueous citric acid solutions, the gross mass that adds water is 17.8 g.Then add 0.2 g hydroxypropyl emthylcellulose and 2 g glycerol, obtain the consolidation liquid of phosphonized chitosan and hydroxypropyl emthylcellulose modification.Be in harmonious proportion by the liquid-solid ratio of 0.5 mL/g by the bone cement powder be made up of bata-tricalcium phosphate and hydroxyapatite in consolidation liquid and embodiment 1, it is 26 min that reference standard ASTM C191 measures the presetting period.Injectability coefficient is 90%.Solidifying bone cement apparent density after 24 hours is 1.48 g/cm
3, in water, defeated and dispersed coefficient is 1.7%, comprcssive strength 3.5 MPa.Be added to the water, solution is in neutral.
Embodiment 8:
Take 0.2 g phosphonized chitosan to join in 10 mL 40 wt% aqueous citric acid solutions, the gross mass that adds water is 19.6 g.Then add 0.2 g hydroxypropyl emthylcellulose and 0.2 g gelatin, obtain phosphonized chitosan, hydroxypropyl emthylcellulose and gelatin modified consolidation liquid.Be in harmonious proportion by the liquid-solid ratio of 0.5 mL/g by the bone cement powder be made up of bata-tricalcium phosphate and hydroxyapatite in consolidation liquid and embodiment 1, it is 15 min that reference standard ASTM C191 measures the presetting period.Injectability coefficient is 98%.Solidifying bone cement apparent density after 24 hours is 1.51 g/cm
3, in water, defeated and dispersed coefficient is 0.7%, comprcssive strength 11.25 MPa.Be added to the water, solution is in neutral.
Embodiment 9:
Take 0.2 g phosphonized chitosan to join in 10 mL 40 wt% aqueous citric acid solutions, the gross mass that adds water is 17.6 g.Then add 0.2 g hydroxypropyl emthylcellulose, 0.2 g gelatin and 2 g glycerol, obtain final consolidation liquid.Be in harmonious proportion by the liquid-solid ratio of 0.5 mL/g by the bone cement powder be made up of bata-tricalcium phosphate and hydroxyapatite in consolidation liquid and embodiment 1, it is 15min that reference standard ASTM C191 measures the presetting period.Injectability coefficient is 98%.Solidifying bone cement apparent density after 24 hours is 1.47 g/cm
3, in water, defeated and dispersed coefficient is 0.5%, comprcssive strength 2.7 MPa.Be added to the water, solution is in neutral.
Claims (1)
1. the preparation method of bone cement consolidation liquid, wherein each constituent mass percentage composition is as follows: citric acid: 3-55%; Phosphonized chitosan: 0.05-10%; Water soluble polymer class total amount is not more than 15%, wherein, sodium carboxymethyl cellulose: 0-5%, hyaluronic acid: 0-1%, hydroxypropyl emthylcellulose: 0-2%, polyvinyl alcohol: 0-1.5%, Polyethylene Glycol: 0-10%, starch: 0-5%, gelatin: 0-2%, collagen protein: 0-2%; Inorganic salts total amount is not more than 20%, wherein, and sodium sulfate: 0-15%, potassium sulfate: 0-15%, ammonium sulfate: 0-15%, magnesium sulfate: 0-10%, sodium chloride: 0-10%, potassium chloride: 0-10%, calcium chloride: 0-15%; Organic molecule class is not more than 45%, wherein, and sodium glycerophosphate: 0-15%, glucose: 0-15%, mannose: 0-15%, cyclodextrin: 0-5%, glycerol: 0-40%; Surplus is water, or acid solution; It is characterized in that, comprise the following steps:
(1) preparation contains the solution of 3-55% citric acid and 0.05-10% phosphonized chitosan;
(2) a kind of or its combination added on the basis of citric acid-chitosan solution in water soluble polymer, inorganic salt or organic molecule modifier obtains final consolidation liquid;
(3) if consolidation liquid for a long time need not, be stored in 4 DEG C of environment, molten in advance before using;
(4) bone cement powder and consolidation liquid are in harmonious proportion by liquid-solid ratio, the bone cement of phosphonized chitosan modification can be obtained;
The solvent of the citrate-phosphate chitosan solution described in step (1) is aqueous solution, or acid solution;
Described acid solution is one in 0.01-0.3 M hydrochloric acid solution, 0.01-0.3 M sulfuric acid solution, 0.01-0.5 M phosphoric acid solution, 0.01-0.6 M acetic acid solution, 0.01-0.2 M salpeter solution, 0.01-0.5 M ascorbic acid solution, 0.01-0.5 M lactic acid solution or its combination;
The bone cement powder that bone cement powder described in step (4) is bata-tricalcium phosphate is main component, hydroxyapatite is auxiliary element, the content of hydroxyapatite is 0.5-49%;
Liquid-solid ratio described in step (4) is the consolidation liquid adding 0.30-0.70 milliliter in every 1 gram of bone cement powder;
The manner of formulation of the solution described in step (2) is room-temperature dissolution, or less than 60 DEG C are heated hydrotropy, can also be aided with mechanical agitation or magnetic agitation;
Pre-molten mode described in step (3) makes consolidation liquid become flowable liquid for heating below 37 DEG C.
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| CN104368042A (en) * | 2014-11-19 | 2015-02-25 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of brushite bone cement |
| CN104491924A (en) * | 2015-01-05 | 2015-04-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of injectable medicine-carrying brushite bone cement |
| CN105327395B (en) * | 2015-11-19 | 2018-07-13 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of acid hydroxy group apatite catalytic curing bone cement |
| CN106075564A (en) * | 2016-08-31 | 2016-11-09 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of magnetic coupling bone cement and preparation method thereof |
| CN106620856A (en) * | 2016-11-08 | 2017-05-10 | 上海纳米技术及应用国家工程研究中心有限公司 | Chemotherapy-thermotherapy type bone repair material on basis of nano-carriers and preparation and application of chemotherapy-thermotherapy type bone repair material |
| CN106552293B (en) * | 2016-11-24 | 2019-11-05 | 南京航空航天大学 | A kind of preparation method of the gluconic acid modified hydroxyapatite bone cement of high intensity |
| US11597859B2 (en) | 2020-01-24 | 2023-03-07 | Oatey Co. | Solvent cement formulations having extended shelf life |
| CN111991615A (en) * | 2020-08-11 | 2020-11-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of lanthanide-doped injectable calcium phosphate bone cement, product and application thereof |
| CN112043870A (en) * | 2020-08-18 | 2020-12-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of 3D-printed polyvinyl alcohol/calcium phosphate drug-loaded bone repair scaffold, product and application thereof |
| CN112107732A (en) * | 2020-09-18 | 2020-12-22 | 成都理工大学 | Anti-scouring high-mineralization-activity composite bone cement and preparation method thereof |
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