CN105233334B - A kind of calcium phosphate bone cement of anti-collapsibility and preparation method thereof, application - Google Patents
A kind of calcium phosphate bone cement of anti-collapsibility and preparation method thereof, application Download PDFInfo
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- CN105233334B CN105233334B CN201510727043.4A CN201510727043A CN105233334B CN 105233334 B CN105233334 B CN 105233334B CN 201510727043 A CN201510727043 A CN 201510727043A CN 105233334 B CN105233334 B CN 105233334B
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Abstract
The invention discloses a kind of calcium phosphate bone cement of anti-collapsibility, is made of calcium phosphate bone cement and galactomannans type natural plant gum；The quality of the galactomannans type natural plant gum is the 0.3~3.0% of calcium phosphate bone cement.The invention also discloses the preparation method and application of the calcium phosphate bone cement of above-mentioned anti-collapsibility.Galactomannans type natural plant gum is successfully applied in calcium phosphate bone cement by the present invention first, meet the anti-collapsibility performance for both significantly increasing calcium phosphate bone cement at the same time, the original curing characteristics of calcium phosphate bone cement and hydrated product and the requirement little to its Effect on Mechanical Properties can be kept again, be effectively improved the success rate of operation.The present invention had not only expanded the new medical value of galactomannans type natural plant gum, but also calcium phosphate bone cement is had broader practice prospect.
Description
Technical field
The present invention relates to bone injury to repair medical material, the calcium phosphate bone cement of more particularly to a kind of anti-collapsibility and its preparation
Method, application.
Background technology
It by calcium phosphate powder is main solid-phase component, deionized water or aqueous solution or blood that calcium phosphate bone cement (CPC), which is,
Deng for liquid phase, solid phase powder and liquid phase are mixed into paste, and raw hydration reaction is issued from solid in room temperature or body temperature environment
Change, the primary product after curing is hydroxyapatite.Due to CPC in chemical composition and the sclerous tissues such as human body bone and tooth
Inorganic constituents is similar, and with good biocompatibility and osteoconductive, can random-shaping, slow releasing carrier of medication can be used as
Deng good characteristic, it has also become one of clinical bone defect healing area research and the hot spot of application.Yet with the material at present still
The shortcomings that come with some shortcomings part, and especially anti-collapsibility (also referred to as water-resistance, rinsing property of anti-impact, anti-washout capacity) is poor, influences
The effect of its clinical practice.
In order to improve the anti-collapsibility of CPC, most common method is to add that some organic polymers and CPC are compound to be increased
The caking property of CPC, so as to strengthen the coherency of paste.(Ishikawa K, Miyamoto Y, the Kon M, et such as Ishikaw
al.Non-decay type fast-setting calcium phosphate cement:composite with sodium
alginate.Biomaterials,1995,16:A certain amount of mosanom 527-532.) is added in solidify liquid, is prepared new
The quick-setting CPC of type, being immediately placed in after reconciliation in water will not be defeated and dispersed, and can normal cure.Takechi etc. (Takechi M,
Miyamoto Y,Ishikawa K,et al.Non-decay type fasting-setting calcium phosphate
cement using chitosan.Journal of Material Science:Materials in Medicine,1996,
7(6):317-322.) find that the CPC for being mixed with chitosan can just prevent the erosion of water, but its machine after mixing 5min with solidify liquid
Tool intensity is slightly below the CPC using sodium alginate.Hydroxypropyl methyl cellulose (HPMC) is dissolved in calcium phosphate bone cement solidify liquid
In, can be made into water proof type CPC with solid phase mixing, (Miao Jun, Liu Chunrong, Xia Qun hydroxypropyl methyl celluloses increase calcium phosphate bone water
The water resistance China's Tissue Engineering Studies and clinical rehabilitation of mud, 2007,11 (5):926-927.).But since HPMC forms class
Net structure like film and the package action to cement, hinder or slow down the hydration rate of CPC, can hinder the knot of bone cement
Crystalline substance, therefore HPMC can make intensity decreases (J Pourchez, A Peschard, P Grosseau, the et al.HPMC of bone cement
and HEMC influence on cement hydration.Cement and Concrete Research,2006,36:
288-294.).In short, although these additives to a certain extent make moderate progress the anti-collapsibility of CPC, but be all the short time
The anti-collapsibility that interior (within 10 minutes) are investigated, and most of hardening time that there is delay CPC and reduce the strong of implant
The problem of spending.
The content of the invention
In order to overcome the disadvantages mentioned above of the prior art and deficiency, it is an object of the present invention to provide a kind of anti-collapsibility
Calcium phosphate bone cement, while the anti-collapsibility performance for not only significantly increasing calcium phosphate bone cement is met, but also calcium phosphate bone can be kept
The original curing characteristics of cement and hydrated product and the requirement little to its Effect on Mechanical Properties.
The second object of the present invention is the preparation method for providing the calcium phosphate bone cement of above-mentioned anti-collapsibility.
The third object of the present invention is the application for providing the calcium phosphate bone cement of above-mentioned anti-collapsibility.
The purpose of the present invention is achieved through the following technical solutions：
A kind of calcium phosphate bone cement of anti-collapsibility, is made of calcium phosphate bone cement and galactomannans type natural plant gum；Institute
The quality for stating galactomannans type natural plant gum is the 0.3~3.0% of calcium phosphate bone cement.
The galactomannans type natural plant gum is at least one in combination of fenugreek gum, guar gum, tara gum, locust bean gum
Kind.
The calcium phosphate bone cement is " tetracalcium phosphate-calcium monohydrogen phosphate " system bone cement, " tetracalcium phosphate-β-tricresyl phosphate
Calcium-calcium dihydrogen phosphate " system bone cement, " type alpha tricalcium phosphate-calcium monohydrogen phosphate-calcium carbonate ", " type alpha tricalcium phosphate-di(2-ethylhexyl)phosphate
Hydrogen calcium-calcium carbonate " system bone cement, " type alpha tricalcium phosphate-tetracalcium phosphate-calcium monohydrogen phosphate " system bone cement, " partially crystallizable
In calcium phosphate-calcium monohydrogen phosphate " system bone cement or " amorphous calcium phosphate-calcium monohydrogen phosphate " system bone cement series bone cement
Any one.
The preparation method of the calcium phosphate bone cement of the anti-collapsibility, calcium phosphate bone cement and galactomannans type are planted
Thing glue mixes, and obtains the calcium phosphate bone cement of anti-collapsibility.
The application of the calcium phosphate bone cement of the anti-collapsibility, is used to prepare bone injury repair material.
It is described preparation bone injury repair material the step of be：
In the ratio of 0.3~0.6mL/g of liquid-solid ratio by deionized water or the calcium phosphate bone cement of solion and anti-collapsibility
Powder uniformly mixes, and reconciles into pastel.
The solion is one kind in physiological saline, phosphate solution, citric acid or citrate solution.
The phosphate solution is dibastic sodium phosphate solution.
The citrate solution is sodium citrate solution.
Compared with prior art, the present invention has the following advantages and beneficial effect：
(1) galactomannans natural plant gum is successfully applied in calcium phosphate bone cement by the present invention first, is significantly improved
The anti-collapsibility performance of calcium phosphate bone cement, anti-collapsibility time can be more than 120 minutes, and anti-collapsibility capacity factor is more than 70%, very
Meet that defeated and dispersed requirement does not occur in the curing process for calcium phosphate bone cement well.And it is not added with galactomannans natural plant gum
The anti-collapsibility time of calcium phosphate bone cement is no more than 10 minutes, and anti-collapsibility capacity factor is less than 50%.
(2) calcium phosphate bone cement of present invention addition galactomannans natural plant gum does not change the note of raw calcium phosphate bone cement
Penetrating property and voluntarily curing characteristics, and do not change the composition of hydrated product after curing (its hydrated product is still hydroxyapatite).
(3) adding for galactomannans natural plant gum of the invention can't be to the mechanical property of calcium phosphate bone cement and solidifying
Tie time generation significant impact.
(4) calcium phosphate bone cement of the natural plant gum containing galactomannans of present invention gained has good biomedicine
Can, more preferable clinical application effect can be obtained.
(5) present invention damages the application extension of galactomannans natural plant gum to calcium phosphate bone cement bioactive bone is prepared
Wound repairs medical material, had both opened up new way to improve the performance of calcium phosphate bone cement, and had also been galactomannans natural plant gum
Open a new application field.Meanwhile the abundance of galactomannans natural plant gum, production cost is low, using gala
Mannosan natural plant gum as calcium phosphate bone cement anti-collapsibility agent compared with other high molecular materials, have cost is low, can give birth to
The advantages such as thing degraded, will produce good economic benefit.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
By combination of fenugreek gum (quality is the 3.0% of tetracalcium phosphate-calcium monohydrogen phosphate bone cement powder) and tetracalcium phosphate-phosphoric acid hydrogen
Calcium bone cement powder uniformly mixes.Then in liquid-solid ratio 0.5mL/g ratio by deionized water solution with it is manufactured in the present embodiment
Calcium phosphate bone cement containing combination of fenugreek gum uniformly mixes, and reconciles into pastel injection mould molding and is placed on 37 DEG C of simulated body fluids
In.The phosphorus of anti-collapsibility calcium phosphate bone cement manufactured in the present embodiment containing combination of fenugreek gum and unused galactomannans natural plant gum
Sour calcium bone cement physicochemical property contrast is as shown in table 1：
Table 1
Note："-" represents the calcium phosphate bone cement for not adding galactomannans natural plant gum；"+" represents to have added galactomannan to gather
The calcium phosphate bone cement of sugared natural plant gum, following table are same.Setting time is with reference to ASTM C191-13 standard tests.Compression strength reference
ISO 9917-1-2007 standard tests.
The calcium phosphate bone cement of anti-collapsibility manufactured in the present embodiment containing combination of fenugreek gum compared with common calcium phosphate bone cement,
Anti-collapsibility coefficient reaches 86 ± 3%, improves more than 2 times, and the anti-collapsibility time increases to be integrated with more than 120min, anti-collapsibility performance
It is obviously improved；Hardening time is 23 ± 3min, has been extended, but is influenced little；Compression strength is also simply declined slightly.
Embodiment 2
By guar gum (quality is the 2.0% of tetracalcium phosphate-bata-tricalcium phosphate-calcium dihydrogen phosphate bone cement) and phosphoric acid
Four calcium-bata-tricalcium phosphate-calcium dihydrogen phosphate bone cement uniformly mixes.Then will in the ratio of liquid-solid ratio 0.4mL/g
0.125mol/L sodium dihydrogen phosphates are uniformly mixed with the calcium phosphate bone cement manufactured in the present embodiment containing guar gum, are reconciled
It is placed on into pastel injection mould molding in 37 DEG C of simulated body fluids.Anti-collapsibility phosphoric acid manufactured in the present embodiment containing guar gum
Calcium bone cement and the contrast of common calcium phosphate bone cement physicochemical property are as shown in table 2：
Table 2
The calcium phosphate bone cement of anti-collapsibility manufactured in the present embodiment containing guar gum compared with common calcium phosphate bone cement,
Anti-collapsibility coefficient reaches 89 ± 3%, improves more than 2 times, and the anti-collapsibility time is also added to overall more than 120min, anti-collapsibility performance
Have clear improvement；Hardening time is 18 ± 1min, has been extended, but is influenced little；There is no significant impact to compression strength.
Embodiment 3
By tara gum (quality is the 1.0% of type alpha tricalcium phosphate-calcium monohydrogen phosphate-calcium carbonate bone cement) and alpha-phosphate three
Calcium-calcium monohydrogen phosphate-calcium carbonate bone cement uniformly mixes.Then in the ratio of liquid-solid ratio 0.5mL/g by 0.25mol/L phosphoric acid hydrogen
Sodium buffer solution is uniformly mixed with the calcium phosphate bone cement manufactured in the present embodiment containing tara gum, reconciles into pastel injection mould
Shaping is placed in 37 DEG C of simulated body fluids.Anti-collapsibility calcium phosphate bone cement manufactured in the present embodiment containing tara gum and common phosphoric acid
The contrast of calcium bone cement physicochemical property is as shown in table 3：
Table 3
The calcium phosphate bone cement of anti-collapsibility manufactured in the present embodiment containing tara gum resists compared with common calcium phosphate bone cement
Defeated and dispersed coefficient reaches 84 ± 1%, improves more than 2 times, and the anti-collapsibility time is also added to be integrated with more than 120min, anti-collapsibility performance
It is obviously improved；Hardening time is 20 ± 0.4min, is influenced less；Compression strength does not also have a great impact.
Embodiment 4
By locust bean gum the 0.5% of partially crystallized calcium phosphate-calcium monohydrogen phosphate bone cement (quality be) and partially crystallized calcium phosphate-
Calcium monohydrogen phosphate bone cement uniformly mixes.Then in liquid-solid ratio 0.3mL/g ratio by physiological saline (0.9% sodium chloride solution) with
Calcium phosphate bone cement manufactured in the present embodiment containing locust bean gum uniformly mixes, and reconciles into pastel injection mould molding and is placed on 37
In DEG C simulated body fluid.Anti-collapsibility calcium phosphate bone cement manufactured in the present embodiment containing locust bean gum and common calcium phosphate bone cement physics and chemistry
Performance comparison is as shown in table 4：
Table 4
The calcium phosphate bone cement of anti-collapsibility manufactured in the present embodiment containing locust bean gum resists compared with common calcium phosphate bone cement
Defeated and dispersed coefficient reaches 88 ± 2%, improves more than 2 times, and the anti-collapsibility time is also added to be integrated with more than 120min, anti-collapsibility performance
It is obviously improved；Hardening time is 26 ± 2min, is influenced less；Compression strength does not also have a great impact.
Embodiment 5
By combination of fenugreek gum (quality is the 0.5% of amorphous calcium phosphate-calcium monohydrogen phosphate bone cement), (quality is nothing to locust bean gum
0.5%) amorphous calcium phosphate-calcium monohydrogen phosphate bone cement is uniformly mixed with amorphous calcium phosphate-calcium monohydrogen phosphate bone cement.Then press
The ratio of liquid-solid ratio 0.5mL/g is by deionized water and the calcium phosphate bone cement manufactured in the present embodiment containing combination of fenugreek gum and locust bean gum
Uniformly mixing, reconciles into pastel injection mould molding and is placed in 37 DEG C of simulated body fluids.It is manufactured in the present embodiment to contain fenugreek
The anti-collapsibility calcium phosphate bone cement of glue and locust bean gum and the contrast of common calcium phosphate bone cement physicochemical property are as shown in table 5：
Table 5
The calcium phosphate bone cement of anti-collapsibility manufactured in the present embodiment containing combination of fenugreek gum and locust bean gum and common calcium phosphate bone
Cement is compared, and anti-collapsibility coefficient reaches 85 ± 2%, is improved more than 2 times, and the anti-collapsibility time is also added to more than 120min, is resisted and is burst
Scattered performance integrally has clear improvement；Hardening time is 33 ± 2min, is influenced less；Compression strength does not also have a great impact.
Embodiment 6
By guar gum (quality is the 1.0% of type alpha tricalcium phosphate-calcium dihydrogen phosphate-calcium carbonate bone cement), locust bean gum
(quality is the 0.3% of type alpha tricalcium phosphate-calcium dihydrogen phosphate-calcium carbonate bone cement) and type alpha tricalcium phosphate-calcium dihydrogen phosphate-
Calcium carbonate bone cement uniformly mixes.Then in the ratio of liquid-solid ratio 0.6mL/g by 2% disodium phosphate soln and the present embodiment system
Standby uniformly mixes containing guar gum with the calcium phosphate bone cement of locust bean gum, reconciles into pastel injection mould molding and is placed on 37
In DEG C simulated body fluid.Anti-collapsibility calcium phosphate bone cement manufactured in the present embodiment containing guar gum and locust bean gum and common calcium phosphate
The contrast of bone cement physicochemical property is as shown in table 6：
Table 6
The calcium phosphate bone cement of anti-collapsibility manufactured in the present embodiment containing guar gum and locust bean gum and common calcium phosphate bone
Cement is compared, and anti-collapsibility coefficient reaches 87 ± 2%, is improved more than 3 times, and the anti-collapsibility time is also added to more than 120min, is resisted and is burst
Scattered performance integrally has clear improvement；Hardening time is 18 ± 0.8min, is influenced less；Compression strength does not also have a great impact.
Embodiment 7
By tara gum (quality is the 0.3% of type alpha tricalcium phosphate-tetracalcium phosphate-calcium monohydrogen phosphate bone cement), locust bean gum (matter
Measure for type alpha tricalcium phosphate-tetracalcium phosphate-calcium monohydrogen phosphate bone cement 0.5%) with type alpha tricalcium phosphate-tetracalcium phosphate-phosphoric acid
Hydrogen calcium bone cement uniformly mixes.Then in the ratio of liquid-solid ratio 0.5mL/g by 0.12mol/L citric acid solutions and the present embodiment system
Standby uniformly mixes containing tara gum with the calcium phosphate bone cement of locust bean gum, reconciles into pastel injection mould molding and is placed on 37 DEG C
In simulated body fluid.Anti-collapsibility calcium phosphate bone cement manufactured in the present embodiment containing tara gum and locust bean gum and common calcium phosphate bone water
The contrast of mud physicochemical property is as shown in table 7：
Table 7
The calcium phosphate bone cement of anti-collapsibility manufactured in the present embodiment containing tara gum and locust bean gum and common calcium phosphate bone water
Mud is compared, and anti-collapsibility coefficient reaches 88 ± 4%, is improved more than 2 times, the anti-collapsibility time is also added to more than 120min, anti-collapsibility
Performance integrally has clear improvement；Hardening time is 18 ± 1.8min, is influenced less；Compression strength does not also have a great impact.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from the embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (4)
1. a kind of calcium phosphate bone cement of anti-collapsibility, it is characterised in that by calcium phosphate bone cement and galactomannans type plant
Glue forms；The quality of the galactomannans type natural plant gum is the 0.3~3.0% of calcium phosphate bone cement；The galactomannan
Glycan type natural plant gum is at least one of combination of fenugreek gum, guar gum, tara gum, locust bean gum；The calcium phosphate bone cement is
" tetracalcium phosphate-calcium monohydrogen phosphate " system bone cement, " tetracalcium phosphate-bata-tricalcium phosphate-calcium dihydrogen phosphate " system bone cement,
" type alpha tricalcium phosphate-calcium monohydrogen phosphate-calcium carbonate ", " type alpha tricalcium phosphate-calcium dihydrogen phosphate-calcium carbonate " system bone cement, " α-
Tricalcium phosphate-tetracalcium phosphate-calcium monohydrogen phosphate " system bone cement, " partially crystallized calcium phosphate-calcium monohydrogen phosphate " system bone cement or
Any one in " amorphous calcium phosphate-calcium monohydrogen phosphate " system bone cement series bone cement.
2. the preparation method of the calcium phosphate bone cement of the anti-collapsibility described in claim 1, it is characterised in that by calcium phosphate bone cement
And the mixing of galactomannans type natural plant gum, obtain the calcium phosphate bone cement of anti-collapsibility.
3. the application of the calcium phosphate bone cement of the anti-collapsibility described in claim 1, it is characterised in that be used to prepare bone injury reparation
Material.
4. the application of the calcium phosphate bone cement of anti-collapsibility according to claim 3, it is characterised in that the preparation bone injury
The step of repair materials is：
In the ratio of 0.3~0.6mL/g of liquid-solid ratio by deionized water or the calcium phoshate bone cement powder of solion and anti-collapsibility
Uniformly mixing, reconciles into pastel；
The solion is one kind in physiological saline, phosphate solution, citric acid or citrate solution；
The phosphate solution is dibastic sodium phosphate solution；
The citrate solution is sodium citrate solution.
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| CN107233627A (en) * | 2017-05-25 | 2017-10-10 | 华南理工大学 | A kind of calcium phosphate bone cement containing konjaku glucomannan and its preparation method and application |
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| CN113769159A (en) * | 2021-08-23 | 2021-12-10 | 广州润虹医药科技股份有限公司 | Anhydrous calcium phosphate bone cement and preparation method thereof |
| CN114772566B (en) * | 2022-05-17 | 2023-08-25 | 深圳市酷彼伴玩具有限公司 | Forming method of hydroxyapatite and hydroxyapatite |
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| GB0311846D0 (en) * | 2003-05-23 | 2003-06-25 | Univ Birmingham | High strength and injectable apatitic calcium phosphate cements |
| CN100391550C (en) * | 2005-10-20 | 2008-06-04 | 华南理工大学 | Method of improving anti collapsibility of calcium phosphate skeletal cement using denaturated starch |
| CN101524557A (en) * | 2009-04-21 | 2009-09-09 | 华南理工大学 | Anti-collapsibility calcium phosphate cement, preparation method and application thereof |
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| CN107233627A (en) * | 2017-05-25 | 2017-10-10 | 华南理工大学 | A kind of calcium phosphate bone cement containing konjaku glucomannan and its preparation method and application |
| CN107233627B (en) * | 2017-05-25 | 2020-08-18 | 华南理工大学 | Calcium phosphate bone cement containing konjac glucomannan as well as preparation method and application thereof |
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