CN108273129B - Anti-collapsibility and high-strength composite calcium phosphate bone cement and preparation method and application thereof - Google Patents
Anti-collapsibility and high-strength composite calcium phosphate bone cement and preparation method and application thereof Download PDFInfo
- Publication number
- CN108273129B CN108273129B CN201810297934.4A CN201810297934A CN108273129B CN 108273129 B CN108273129 B CN 108273129B CN 201810297934 A CN201810297934 A CN 201810297934A CN 108273129 B CN108273129 B CN 108273129B
- Authority
- CN
- China
- Prior art keywords
- calcium phosphate
- chitosan
- cement
- solution
- phosphate cement
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, 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
- A61L27/14—Macromolecular materials
- A61L27/20—Polysaccharides
-
- 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
-
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Dermatology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Inorganic Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention belongs to the field of medical materials for repairing bone injury, and discloses anti-collapsibility and high-strength composite calcium phosphate bone cement and a preparation method and application thereof. The composite calcium phosphate cement comprises calcium phosphate cement and 0.2-3% of hydroxypropyl benzoic acid-g-chitosan by mass; the hydroxypropyl benzoic acid-g-chitosan is obtained by coupling 3, 4-dihydroxyphenyl propionic acid or 3, 4-dihydroxyphenyl acetic acid with chitosan. Compared with the common calcium phosphate cement, the composite calcium phosphate cement has better biocompatibility, improves the strength, the anti-collapsibility and the biocompatibility of the calcium phosphate cement by utilizing the superior adhesion performance of the Dopa-CS and the good biocompatibility of the CS, can also keep the original curing characteristic of the calcium phosphate cement, has little influence on the curing time, obviously improves the anti-collapsibility and the compressive strength, and can be applied to the field of bone injury repair.
Description
Technical Field
The invention belongs to the field of medical materials for repairing bone injury, and particularly relates to anti-collapsibility and high-strength composite calcium phosphate bone cement and a preparation method and application thereof.
Background
The artificial bone repair of bone defects is a brand new treatment mode and is one of the hot problems in the current medical research. The Calcium Phosphate Cement (CPC) is composed of one or more solid calcium phosphate powders and solidifying liquid, and can be self-solidified under physiological condition, its solidified product is very similar to inorganic component of bone tissue, and its crystal phase structure is also similar to bone tissue. More importantly, the material can be easily injected and adapted to the shape of the defect, can be gradually degraded after being implanted into the bone defect part, avoids the pain of the secondary operation and has remarkable superiority and wide market in the clinical application of bone repair. However, the material system has the defects of insufficient mechanical strength, poor toughness, particularly poor collapsibility resistance, capability of being dispersed by blood in an operation in the injection process and the like, so that the improvement of the mechanical property and the collapsibility resistance of the calcium phosphate cement system becomes the main direction of the future development of the CPC cement system.
At present, a plurality of researchers improve the anti-collapse performance of the bone cement by adding organic polymer materials, and Ishikawa et al (Ishikawa, K.et al biomaterials, (1995)16(7): 527-. Takechi et al (Takechi, M.et al.J. Mater Sci: Mater Med (1996)7:317.) found that the addition of chitosan to bone cement not only improves the anti-collapse properties of bone cement, but also has better osteoconductivity and bioactivity, but also has lower mechanical strength than bone cement with sodium alginate. In summary, the above additives improve the anti-collapse properties of the bone cement to some extent, but do not maintain their original curing properties and reduce the strength of the implant.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art that the calcium phosphate cement cannot be self-cured or collapsed due to soaking and washing of body fluid before self-curing in the injection process, the invention provides a composite calcium phosphate cement with collapse resistance and high strength. The calcium phosphate bone cement has good comprehensive performance, high compression strength and good collapsibility resistance, realizes the improvement of collapsibility resistance and does not reduce the compression strength of the calcium phosphate bone cement.
The invention also aims to provide a preparation method of the anti-collapse and high-strength composite calcium phosphate cement.
The invention further aims to provide application of the anti-collapse and high-strength composite calcium phosphate bone cement in the field of bone injury repair.
The purpose of the invention is realized by the following scheme:
an anti-collapse and high-strength composite calcium phosphate cement composition comprises calcium phosphate cement and 0.2-3% of hydroxypropyl benzoic acid-g-chitosan (Dopa-CS) by mass. The hydroxypropyl benzoic acid-g-chitosan is obtained by coupling 3, 4-dihydroxyphenyl propionic acid or 3, 4-dihydroxyphenyl acetic acid with chitosan.
The grafting rate of the hydroxypropyl benzoic acid-g-chitosan is preferably 5-30%, and more preferably 7-15%.
The hydroxypropyl benzoic acid-g-chitosan is obtained by performing acylation reaction on 3, 4-dihydroxyphenyl propionic acid or 3, 4-dihydroxyphenyl acetic acid and chitosan, which are conventional in the field. The preparation method specifically comprises the following steps: dissolving chitosan in acid liquor, and adjusting the pH value to 4-5; dissolving 3, 4-dihydroxyphenyl propionic acid or 3, 4-dihydroxyphenyl acetic acid and carbodiimide hydrochloride in an ethanol solution, adding the ethanol solution into the chitosan solution, and stirring for reaction to obtain the hydroxypropanebenzoic acid-g-chitosan.
The molar ratio of the chitosan to the 3, 4-dihydroxyphenyl propionic acid or the 3, 4-dihydroxyphenyl acetic acid is 1: 0.2-1: 2.
the volume ratio of water to absolute ethyl alcohol in the ethyl alcohol solution is preferably 1: 1.
The acid solution is preferably hydrochloric acid solution, and more preferably 1M hydrochloric acid solution.
The pH adjustment can be carried out using a basic solution, such as sodium hydroxide solution, preferably 5M sodium hydroxide solution.
The stirring reaction may be carried out at room temperature. In the stirring reaction process, the pH is preferably kept to be 4.5-5.0.
The product after the stirring reaction can be dialyzed in HCl solution with pH 5 and water, respectively, and lyophilized to obtain a purified product.
The hydroxypropyl benzoic acid-g-chitosan can be prepared into a solution and then mixed with the calcium phosphate cement to obtain the anti-collapsibility and high-strength composite calcium phosphate cement.
The concentration of the solution is preferably 0.1-3 wt%. The solvent of the solution is preferably a citric acid solution, more preferably a 0.1M citric acid solution.
In the present invention, the calcium phosphate cement may be one conventionally used in the art, and may be at least one of "α -tricalcium phosphate-calcium hydrogen phosphate-calcium carbonate" system cement, "α -tricalcium phosphate-monocalcium phosphate-calcium carbonate" system cement, "α -tricalcium phosphate-tetracalcium phosphate-calcium hydrogen phosphate" system cement, or "α -tricalcium phosphate-monocalcium phosphate" system cement.
The invention also provides a preparation method of the anti-collapsibility and high-strength composite calcium phosphate cement. In particular to a calcium phosphate bone cement and hydroxypropyl benzoic acid-g-chitosan which are mixed evenly.
The hydroxypropyl benzoic acid-g-chitosan can be prepared into a solution and then mixed with the calcium phosphate cement to obtain the anti-collapsibility and high-strength composite calcium phosphate cement.
The concentration of the solution is preferably 0.1-3 wt%. The solvent of the solution is preferably a citric acid solution, more preferably a 0.1M citric acid solution.
Further, the preparation method specifically comprises the steps of dissolving the hydroxypropyl benzoic acid-g-chitosan in 0.1M citric acid solution to obtain a solution with the concentration of 0.1-3 wt%, and mixing the solution with the calcium phosphate bone cement to obtain the anti-collapse and high-strength composite calcium phosphate bone cement.
The mass-volume ratio of the calcium phosphate cement to the solution is preferably g/mL, 1: 0.3-1: 0.7.
Compared with the common calcium phosphate cement, the anti-collapsibility and high-strength composite calcium phosphate cement has better biocompatibility, does not prolong the curing time, obviously improves the anti-collapsibility and compressive strength, and can be applied to the field of bone injury repair. The composite calcium phosphate cement of the present invention is implanted into the operation site directly via medical apparatus for clinical application.
The anti-collapse and high-strength composite calcium phosphate bone cement is added with the Dopa-CS with good biocompatibility, degradability and bonding performance on the basis of common calcium phosphate bone cement, and the strength, anti-collapse performance and biocompatibility of the calcium phosphate bone cement are improved by skillfully utilizing the superior adhesion performance of the Dopa-CS and the good biocompatibility of the CS. The calcium phosphate cement has the advantages that the Chitosan (CS) has a series of excellent performances to obtain better biocompatibility, the hydroxypropyl benzoic acid (Dopa) dopamine structure has adhesion performance to greatly improve the anti-collapsibility and compressive strength of the calcium phosphate cement, the original curing characteristic of the calcium phosphate cement can be maintained, and the curing time of the calcium phosphate cement is not greatly influenced.
The anti-collapse and high-strength composite calcium phosphate bone cement can bring better biomedical functions for bone injury repair medical materials, can obtain better clinical application effect, and has good application prospect.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention successfully applies the Dopa-CS to the calcium phosphate cement for the first time, and the obtained composite bone cement not only keeps the characteristic of short curing time, but also obviously improves the anti-collapsibility of the calcium phosphate cement: the anti-collapse time is more than 120 minutes, the anti-collapse capability coefficient is more than 70 percent, and the requirement that the calcium phosphate cement does not collapse in the curing process is well met. The anti-collapse time of the calcium phosphate bone cement without adding the Dopa-CS is not more than 10 minutes, and the anti-collapse capability coefficient is less than 40 percent.
(2) The addition of Dopa-CS does not change the self-curing property of the original calcium phosphate cement and the composition of a hydration product after curing (the hydration component is hydroxyapatite).
(3) Tests prove that the addition of the Dopa-CS in the invention greatly improves the mechanical properties of the calcium phosphate cement.
(4) The calcium phosphate bone cement containing Dops-CS obtained by the invention has good biomedical performance, can obtain better clinical application effect and has good application prospect.
(5) The invention expands the application of the Dopa-CS to the preparation of the bioactive bone injury repair medical material of the calcium phosphate bone cement, develops a new way for improving the performance of the calcium phosphate bone cement, and develops a new application field for the Dopa-CS. Meanwhile, the chitosan has rich sources, the reaction with the Dopa is simple and controllable, and the biological performance of the Dopa-CS is excellent. Compared with other high polymer materials, the Dopa-CS adopted as the calcium phosphate cement anti-collapsibility agent has the advantages of biodegradability, good biocompatibility and the like, and can generate good social benefit and economic benefit.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The materials referred to in the following examples are commercially available.
The monocalcium phosphate, the calcium hydrophosphate, the tetracalcium phosphate and the calcium carbonate used in the embodiment of the invention are all commercially available chemical raw materials, and are subjected to ball milling treatment until the particle size is 10-50 micrometers.
The α -tricalcium phosphate (α -TCP) used in the examples is commercially available or can be prepared by a solid phase reaction sintering process: according to the weight ratio of 2.13: 1, weighing calcium hydrophosphate and calcium carbonate powder according to the molar ratio, uniformly mixing, carrying out wet ball milling, centrifuging, drying, calcining for 1h at 900 ℃, and grinding through a 0.5mm sieve. And then placing the powder in a muffle furnace, calcining to 1350 ℃, preserving heat for 4 hours, quenching to room temperature in air, carrying out ball milling on the powder, and sieving by a 125-micron sieve to obtain the alpha-TCP powder.
Preparation of hydroxypropanebenzoic acid-g-chitosan (Dopa-CS):
the chitosan-modified starch is prepared by coupling chitosan and 3, 4-dihydroxyphenyl propionic acid or 3, 4-dihydroxyphenyl acetic acid, and specifically comprises the following steps: dissolving chitosan in 0.5-1M HCl solution, adding water after completely dissolving, and adjusting pH to 4-5 with 3-5M NaOH solution. 3, 4-dihydroxyphenylpropionic acid or 3, 4-dihydroxyphenylacetic acid and carbodiimide hydrochloride were dissolved in water and an anhydrous ethanol solution (1:1-1:2, v/v), and slowly added to the above chitosan solution. The reaction solution is stirred vigorously at room temperature for 6-24h, keeping the pH of the solution at 4.0-5.0. After the reaction, the reaction product was dialyzed against HCl solution at pH 5 and water for 2 days, respectively, and the final product was stored in a dry box by freeze-drying.
By adjusting the dosage ratio of chitosan and 3, 4-dihydroxyphenyl propionic acid or 3, 4-dihydroxyphenyl acetic acid and the reaction time, the Dopa-CS with different grafting ratios can be obtained, and the grafting ratio can be used1H NMR measurement.
Example 1:
1. preparation of calcium phosphate bone cement
Dissolving Dopa-CS (the grafting rate is 10%) in 0.1M citric acid solution to prepare 0.5% Dopa-CS solution, then uniformly mixing the Dopa-CS solution with 1g of calcium phosphate cement powder (alpha-tricalcium phosphate-calcium hydrophosphate-calcium carbonate) according to the liquid-solid ratio of 0.5mL/g, blending to paste, injecting the paste into a mould for forming, and detecting.
2. Physical and chemical property detection
And (3) detecting the physicochemical property of the bone cement prepared in the step (1) and bone cement without adding Dopa-CS.
(1) Curing time test
The cure time test was performed according to American society for testing and materials Standard ASTM C190-03. The weight of the Vicat instrument pressure head is 300 plus or minus 0.5g, and the diameter of the needle head is 1 plus or minus 0.05 mm. The test procedure was as follows: filling the mixed paste into a cylindrical die with the diameter of 8mm multiplied by 12mm for molding, putting the die into a constant-temperature and constant-humidity box with the temperature of 37 ℃ and the humidity of 100 percent, starting timing from the beginning of adding the curing liquid, loosening a pressure head, freely sinking a test needle into the slurry, and observing the indication value of the pointer. The measurement was performed every 30 seconds. And when the test needle has no obvious indentation on the surface of the sample, the required time is the curing time. Each set of samples was run in duplicate for 6 runs and the mean and standard deviation calculated.
(2) Test for compressive Strength
Filling the mixed paste into a cylindrical die with the diameter of 8mm multiplied by 12mm for molding, immediately pressing for 5 seconds at the pressure of 700kPa to discharge residual large bubbles in the sample, then placing the sample in a constant temperature and humidity box with the temperature of 37 ℃ and the humidity of 100% for curing, demolding after curing for a certain time, and testing the compressive strength of the sample on a universal mechanical testing machine with the loading speed of 1 mm/min. Each set of samples was run in duplicate for 6 runs and the mean and standard deviation calculated.
(3) Resistance to collapse test
Filling the mixed paste into a cylindrical die with the diameter of 8mm multiplied by 12mm for molding, putting the molded die into simulated body fluid after 5 minutes, and then putting the molded die into a shaking table. Taking the dispersion of the particles generated by the bone cement sample as a collapsibility mark, recording the anti-collapsibility time and the percentage of the mass left after the calcium phosphate bone cement slurry is solidified in the simulated body fluid environment to the total mass of the calcium phosphate bone cement before solidification. Each set of samples was assayed in parallel 6 times. The mean and standard deviation were calculated.
The physicochemical performance of the anti-collapse and high strength calcium phosphate cement containing Dopa-CS prepared in this example versus normal alpha-tricalcium phosphate-calcium hydrogen phosphate-calcium carbonate cement is shown in table 1:
TABLE 1 physicochemical Properties
Note: "-" indicates calcium phosphate cement without addition of Dopa-CS; "+" indicates a calcium phosphate cement with the addition of Dopa-CS, as shown in the table below.
Compared with the common calcium phosphate cement, the anti-collapse coefficient of the high-strength calcium phosphate cement containing the Dopa-CS prepared by the embodiment reaches 79 +/-3%, the anti-collapse time is prolonged to be more than 120min, and the anti-collapse performance is improved remarkably on the whole; the curing time is 14 +/-0.8 min, and the influence is small; the compressive strength reaches 23 +/-1.7 MPa, and the mechanical property is obviously improved.
Example 2:
dissolving Dopa-CS (the grafting rate is 7%) in 0.1M citric acid solution to prepare 1% Dopa-CS solution, then uniformly mixing the Dopa-CS solution with 1g of calcium phosphate cement powder (alpha-tricalcium phosphate-monocalcium phosphate-calcium carbonate) according to the liquid-solid ratio of 0.6mL/g, blending to paste, injecting the paste into a mold for molding, and detecting. The detection method and procedure were the same as in example 1.
The physicochemical performance of the anti-collapse and high-strength calcium phosphate cement containing Dopa-CS prepared in this example versus ordinary α -tricalcium phosphate-monocalcium phosphate-calcium carbonate cement is shown in table 2:
TABLE 2 physicochemical Properties
Compared with the common calcium phosphate cement, the collapse resistance coefficient of the high-strength calcium phosphate cement containing the Dopa-CS prepared by the embodiment reaches 81 +/-3%, the collapse resistance time is prolonged to be more than 120min, and the collapse resistance performance is improved obviously on the whole; the curing time is 19 +/-1.2 min, and the influence is small; the compressive strength reaches 23 +/-2.1 MPa, and the mechanical property is obviously improved.
Example 3:
dissolving Dopa-CS (the grafting rate is 10%) in 0.1M citric acid solution to prepare 2% Dopa-CS solution, then uniformly mixing the Dopa-CS solution with 1g of calcium phosphate cement powder (alpha-tricalcium phosphate-monocalcium phosphate-calcium carbonate) according to the liquid-solid ratio of 0.4mL/g, blending to paste, injecting the paste into a mold for molding, and detecting. The detection method and procedure were the same as in example 1.
The physicochemical performance of the anti-collapse and high-strength calcium phosphate cement containing Dopa-CS prepared in this example versus ordinary α -tricalcium phosphate-monocalcium phosphate-calcium carbonate cement is shown in table 3:
TABLE 3 physicochemical Properties
Compared with the common calcium phosphate cement, the collapse resistance coefficient of the high-strength calcium phosphate cement containing the Dopa-CS prepared by the embodiment reaches 85 +/-4%, the collapse resistance time is prolonged to be more than 120min, and the collapse resistance performance is improved obviously on the whole; the curing time is 17 +/-1.1 min, and the influence is small; the compressive strength reaches 28 +/-1.7 MPa, and the mechanical property is obviously improved.
Example 4:
dissolving Dopa-CS (the grafting rate is 13%) in 0.1M citric acid solution to prepare 1% Dopa-CS solution, then uniformly mixing the Dopa-CS solution with 1g of calcium phosphate cement powder (alpha-tricalcium phosphate-tetracalcium phosphate-calcium hydrophosphate) according to the liquid-solid ratio of 0.5mL/g, blending to paste, injecting the paste into a mold for molding, and detecting. The detection method and procedure were the same as in example 1.
The physicochemical properties of the anti-collapse and high strength calcium phosphate cement containing Dopa-CS prepared in this example versus normal alpha-tricalcium phosphate-tetracalcium phosphate-dicalcium phosphate cement are shown in table 4:
TABLE 4 physicochemical Properties
Compared with the common calcium phosphate cement, the collapse resistance coefficient of the high-strength calcium phosphate cement containing the Dopa-CS prepared by the embodiment reaches 83 +/-4%, the collapse resistance time is prolonged to be more than 120min, and the collapse resistance performance is improved remarkably on the whole; the curing time is 18 +/-1 min, and the influence is little; the compressive strength reaches 33 +/-2.4 MPa, and the mechanical property is obviously improved.
Example 5:
dissolving Dopa-CS (the grafting rate is 13%) in 0.1M citric acid solution to prepare 3% Dopa-CS solution, then uniformly mixing the Dopa-CS solution with 1g of calcium phosphate cement powder (alpha-tricalcium phosphate-monocalcium phosphate) according to the liquid-solid ratio of 0.6mL/g, blending to paste, injecting the paste into a mould for forming, and detecting. The detection method and procedure were the same as in example 1.
The physicochemical performance of the anti-collapse and high strength calcium phosphate cement containing Dopa-CS prepared in this example versus normal alpha-tricalcium phosphate-monocalcium phosphate cement is shown in table 5:
TABLE 5 physicochemical Properties
Compared with the common calcium phosphate cement, the collapse resistance coefficient of the high-strength calcium phosphate cement containing the Dopa-CS prepared by the embodiment reaches 83 +/-4%, the collapse resistance time is prolonged to be more than 120min, and the collapse resistance performance is improved remarkably on the whole; the curing time is 20 +/-1.2 min, and the influence is small; the compressive strength reaches 24 +/-1.8 MPa, and the mechanical property is obviously improved.
Example 6:
dissolving Dopa-CS (the grafting rate is 20%) in 0.1M citric acid solution to prepare 0.5% Dopa-CS solution, then uniformly mixing the Dopa-CS solution with 1g of calcium phosphate bone cement powder (alpha-tricalcium phosphate-monocalcium phosphate) according to the liquid-solid ratio of 0.4mL/g, blending to paste, injecting the paste into a mold for molding, and detecting. The detection method and procedure were the same as in example 1.
The physicochemical performance pairs of the anti-collapse and high-strength calcium phosphate cement containing Dopa-CS prepared in this example and the ordinary α -tricalcium phosphate-monocalcium phosphate cement are shown in table 6:
TABLE 6 physicochemical Properties
Compared with the common calcium phosphate cement, the collapse resistance coefficient of the high-strength calcium phosphate cement containing the Dopa-CS prepared by the embodiment reaches 80 +/-4%, the collapse resistance time is prolonged to be more than 120min, and the collapse resistance performance is improved obviously on the whole; the curing time is 17 +/-1 min, and the influence is little; the compressive strength reaches 26 +/-2 MPa, and the mechanical property is obviously improved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. The composite calcium phosphate cement composition with the advantages of collapse resistance and high strength is characterized in that: comprises calcium phosphate cement and 0.2-3% of hydroxypropyl benzoic acid-g-chitosan by mass;
the hydroxypropyl benzoic acid-g-chitosan is obtained by coupling 3, 4-dihydroxyphenyl propionic acid or 3, 4-dihydroxyphenyl acetic acid with chitosan;
the grafting rate of the hydroxypropyl benzoic acid-g-chitosan is 5-30%;
the hydroxypropyl benzoic acid-g-chitosan is prepared by performing acylation reaction on 3, 4-dihydroxyphenyl propionic acid or 3, 4-dihydroxyphenyl acetic acid and chitosan, and is specifically prepared by the following method: dissolving chitosan in acid liquor, and adjusting the pH value to 4-5; dissolving 3, 4-dihydroxyphenyl propionic acid or 3, 4-dihydroxyphenyl acetic acid and carbodiimide hydrochloride in an ethanol solution, adding the ethanol solution into the chitosan solution, and stirring for reaction to obtain hydroxypropanoic acid-g-chitosan;
the calcium phosphate bone cement is at least one of alpha-tricalcium phosphate-calcium hydrogen phosphate-calcium carbonate system bone cement, alpha-tricalcium phosphate-monocalcium phosphate-calcium carbonate system bone cement, alpha-tricalcium phosphate-tetracalcium phosphate-calcium hydrogen phosphate system bone cement and alpha-tricalcium phosphate-monocalcium phosphate system bone cement.
2. The collapse resistant and high strength composite calcium phosphate cement composition according to claim 1, wherein: the molar ratio of the chitosan to the 3, 4-dihydroxyphenyl propionic acid or the 3, 4-dihydroxyphenyl acetic acid is 1: 0.2-1: 2.
3. the collapse resistant and high strength composite calcium phosphate cement composition according to claim 1, wherein: and in the stirring reaction process, the pH is kept to be 4.5-5.0.
4. The collapse resistant and high strength composite calcium phosphate cement composition according to claim 1, wherein: and (3) preparing the hydroxypropyl benzoic acid-g-chitosan into a solution, and mixing the solution with the calcium phosphate cement to obtain the anti-collapsibility and high-strength composite calcium phosphate cement composition.
5. The collapse resistant and high strength composite calcium phosphate cement composition according to claim 4, wherein: the concentration of the solution is 0.1-3 wt%; the solvent of the solution is citric acid solution.
6. A preparation method of the anti-collapse and high-strength composite calcium phosphate cement composition as claimed in any one of claims 1 to 5, which is characterized in that the composition is obtained by uniformly mixing calcium phosphate cement and hydroxypropyl benzoic acid-g-chitosan.
7. Use of the anti-collapse and high-strength composite calcium phosphate cement composition according to any one of claims 1 to 5 in the field of preparation of bone injury repair materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810297934.4A CN108273129B (en) | 2018-03-30 | 2018-03-30 | Anti-collapsibility and high-strength composite calcium phosphate bone cement and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810297934.4A CN108273129B (en) | 2018-03-30 | 2018-03-30 | Anti-collapsibility and high-strength composite calcium phosphate bone cement and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108273129A CN108273129A (en) | 2018-07-13 |
| CN108273129B true CN108273129B (en) | 2020-12-11 |
Family
ID=62811380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810297934.4A Active CN108273129B (en) | 2018-03-30 | 2018-03-30 | Anti-collapsibility and high-strength composite calcium phosphate bone cement and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108273129B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101524557A (en) * | 2009-04-21 | 2009-09-09 | 华南理工大学 | Anti-collapsibility calcium phosphate cement, preparation method and application thereof |
| CN102526798A (en) * | 2012-01-18 | 2012-07-04 | 华东理工大学 | Injectable compound bone cement and preparation method thereof |
| CN104353122A (en) * | 2014-11-24 | 2015-02-18 | 吴志宏 | 3D printed porous metal with bionic three-dimensional (3D) micro-scaffold and preparation method of 3D printed porous metal |
| CN105327395A (en) * | 2015-11-19 | 2016-02-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of bone cement catalytically cured by acidic HA (hydroxyapatite) |
| CN107050508A (en) * | 2017-01-19 | 2017-08-18 | 深圳清华大学研究院 | Injectable bone repair material and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005046530A (en) * | 2003-07-31 | 2005-02-24 | National Institute Of Advanced Industrial & Technology | Porous calcium phosphate hardened body, method of manufacturing the same, and artificial bone and medicine controlled release body using the same |
-
2018
- 2018-03-30 CN CN201810297934.4A patent/CN108273129B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101524557A (en) * | 2009-04-21 | 2009-09-09 | 华南理工大学 | Anti-collapsibility calcium phosphate cement, preparation method and application thereof |
| CN102526798A (en) * | 2012-01-18 | 2012-07-04 | 华东理工大学 | Injectable compound bone cement and preparation method thereof |
| CN104353122A (en) * | 2014-11-24 | 2015-02-18 | 吴志宏 | 3D printed porous metal with bionic three-dimensional (3D) micro-scaffold and preparation method of 3D printed porous metal |
| CN105327395A (en) * | 2015-11-19 | 2016-02-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of bone cement catalytically cured by acidic HA (hydroxyapatite) |
| CN107050508A (en) * | 2017-01-19 | 2017-08-18 | 深圳清华大学研究院 | Injectable bone repair material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《多孔磷酸钙/骨基质明胶复合骨水泥修复兔腰椎骨缺损的实验研究》;王松等;《骨与关节修复重建》;20171231;第31卷(第12期);第1462-1467页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108273129A (en) | 2018-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Qi et al. | Improved injectability and in vitro degradation of a calcium phosphate cement containing poly (lactide-co-glycolide) microspheres | |
| CN108635624B (en) | Anti-collapsibility injectable magnesium phosphate-based bone cement | |
| CN107303397B (en) | A kind of biologically active Injectable compound bone cement and its preparation method and application | |
| US20060173551A1 (en) | Tissue augmentation material and method | |
| CN101053673B (en) | High strength and tenacity degradable strontium calcium superphosphate composite bone cement and its preparation method | |
| CN108273131B (en) | Composite bone cement, preparation method and application thereof, and bone repair material | |
| AU6905100A (en) | Tissue augmentation material and methods | |
| CN104591679A (en) | Modified magnesium oxychloride bone cement as well as preparation method and application thereof | |
| CN113384746B (en) | Bone cement composite material and preparation method thereof | |
| CN109331223B (en) | Medicine-carrying bioactive glass composite calcium phosphate bone cement and application thereof | |
| CN109106986B (en) | Medicine controlled-release calcium phosphate bone cement composite microsphere, preparation method and application thereof | |
| CN108653804B (en) | Preparation method of silicon-doped calcium phosphate bone repair material | |
| CN107233627B (en) | Calcium phosphate bone cement containing konjac glucomannan as well as preparation method and application thereof | |
| Qi et al. | Mechanical and rheological properties and injectability of calcium phosphate cement containing poly (lactic-co-glycolic acid) microspheres | |
| CN108273129B (en) | Anti-collapsibility and high-strength composite calcium phosphate bone cement and preparation method and application thereof | |
| CHANG et al. | An injectable composite bone cement based on mesoporous borosilicate bioactive glass spheres | |
| CN107412874B (en) | Injectable calcium sulfate hemihydrate/octacalcium phosphate/sodium hyaluronate sulfate composite artificial bone material and preparation method thereof | |
| CN113082296B (en) | Calcium phosphate bone cement with good injectability and preparation method thereof | |
| CN109939261B (en) | Curing liquid capable of regulating and controlling injection property of calcium phosphate bone cement and preparation method and application thereof | |
| CN110665056B (en) | Injectable bone cement with tissue self-bonding performance and preparation method and application thereof | |
| CN108159487A (en) | The preparation method of α-half-H 2 O calcium sulphate people's bone material | |
| Nezafati et al. | EVALUATION OF A PREPARED SOL-GEL BIOACTIVE GLASS FIBRE-REINFORCED CALCIUM PHOSPHATE CEMENT | |
| CN108273128B (en) | Self-curing calcium phosphate bone repair material | |
| CN111012946A (en) | Thermo-sensitive calcium phosphate bone cement and preparation method thereof | |
| CN109260523A (en) | A kind of calcium phosphate bone cement complex microsphere and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |