CN109125804A - A kind of solidify liquid and the preparation method and application thereof suitable for calcium orthophosphate base bone cement - Google Patents
A kind of solidify liquid and the preparation method and application thereof suitable for calcium orthophosphate base bone cement Download PDFInfo
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- CN109125804A CN109125804A CN201811215210.7A CN201811215210A CN109125804A CN 109125804 A CN109125804 A CN 109125804A CN 201811215210 A CN201811215210 A CN 201811215210A CN 109125804 A CN109125804 A CN 109125804A
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- 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
- A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
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- 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
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- 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
Abstract
The solidify liquid and the preparation method and application thereof that the present invention provides a kind of suitable for calcium orthophosphate base bone cement.The solidify liquid suitable for calcium orthophosphate base bone cement includes the following component being calculated by mass percentage: citric acid 2~9%；PVP 1~6%；Phosphate 5~25%；PVA 1~5%.The creatively ingenious phosphate that is utilized of the present invention is to the promotion ability of early hydration product；The acidic environment of citric acid provides；The numerator mediated effect that PVP deposits synthos；The water conservation sexual function of PVA, pass through the synergistic effect of citric acid, phosphate, PVP and PVA, significantly improve the mechanical performances such as calcium phosphate bone cement ability to cure, early strength and later strength, the medical value of calcium phosphate bone cement is expanded, the use standard for making calcium phosphate bone cement more approach clinic simultaneously, has broad application prospects.
Description
Technical field
The invention belongs to bone injuries to repair field of medical materials, in particular to a kind of consolidating suitable for calcium orthophosphate base bone cement
Change liquid and the preparation method and application thereof.
Background technique
The powder and solidify liquid that calcium phosphate bone cement (CPC) is mixed by one or more of synthos form, when use
The two reconciles according to a certain percentage, can voluntarily solidify under room temperature or human body environment and plasticity, ingredient pass through hydration reaction most
It is converted mainly into hydroxyapatite (HA) eventually, bone uptake can be guided, is gradually absorbed by tissue and generates bone tissue regeneration effect,
With good biocompatibility, before having huge clinical application superiority and wide market in terms of the bone defect healing
Scape, but there are still shortcomings for the material, and especially it is not easy quickly to be cured during being implanted into human body, reduces
Intensity after material implantation, and it is likely to result in treatment failure, limit the application of the material.Therefore how calcium phosphate is improved
The solidification rate and solidification early strength performance of bone cement are to realize that it is applied to clinical and gives full play to its bone defect healing function
The important foundation of energy.
Researcher mainly improves calcium phosphate addition nucleus (HA) and its by way of adding other solid phase additives at present
The hydration efficiency of bone cement；Marc Bohner proposes that current calcium phosphate bone cement system mainly passes through regulation aquation powder
Granularity and the curing reaction for improving calcium phosphate bone cement by addition solid phase additive.The solidification of relatively common CPC promotes
Agent is Na2HPO4And NaH2PO4Equal inorganic salts substance, can be effectively shortened using its aqueous solution as solidify liquid CPC solidification when
Between.Miyamoto etc. is prepared for a kind of type CPC solidifying fastly using neutral sodium radio-phosphate,P-32 solution, experiments have shown that its setting time in vivo
It shortens 5~7 minutes.Isikawa etc. also compares the curing time of tetracalcium phosphate type bone cement mixed phosphate sodium solution, discovery
Its curing time can be shortened 5 minutes.But sodium ascorbyl phosphate will affect the intensity of CPC solidified body especially to the promotion of setting time
It is early strength, influences the progress of hydration process because the crystal quickly generated can be attached to the surface of aquation raw material.In addition
Calcium carbonate and calcium sulfate are also used as the curing accelerator of CPC；The reaction mechanism of calcium carbonate and calcium sulfate is that it is solidifying
Partial Liquid Phase moisture is consumed in the process, is caused liquid-solid ratio to reduce indirectly and is played and promote solidifying effect, has one to curing reaction
Fixed negative role；Organic acid such as polyacrylic acid etc. also has certain blood coagulation enhancing effect, and most of mechanism is shown as in same CPC
Acid-base neutralization reaction occurs for alkaline matter, and solidification forms hydrogel quickly；And the presence of water gel will form space obstacle,
Influence the mechanical performance of solidified body.
Specific to setting time, the report of research is relatively more, but the raising of setting time not necessarily promotes admittedly
Change the progress of reaction；Because simple raising setting time will affect the hydration process of calcium phosphate bone cement system, and then influence
To the intensity of bone cement solidified body.Phosphatic curing reaction rate how is effectively facilitated, makes calcium phosphate bone cement in humidity
Have quick respond under environment and its mechanical strength of early stage is that face one of current calcium phosphate bone cement is important
Challenge；The requirement for clinically rushing ability to the anti-blood of CPC simultaneously is relatively high, and quickly and effectively carrying out hydration reaction is to improve
The anti-blood of bone cement slurry rushes the effective measures of ability.To sum up, although current research achievement can improve calcium phosphate bone cement
Hydrating capacity, but most of additives exist and shorten calcium phosphate bone cement curing time but to reduce solidified body premature cure strong
The problem of spending；There is no the hydration reaction abilities that the raising CPC of the angle essence from hydration reaction solidifies raw material.
Summary of the invention
The primary purpose of the present invention is that improving the ability to cure and its early strength of calcium phosphate bone cement；Overcome existing skill
In art calcium phosphate bone cement before self-curing by the immersion of body fluid and washing away can postpone calcium phosphate bone cement curing time and
The shortcoming for reducing implant intensity, provides a kind of solidify liquid suitable for calcium orthophosphate base bone cement.
Another object of the present invention is to provide the preparation methods of the solidify liquid suitable for calcium orthophosphate base bone cement.
A further object of the present invention is to provide the applications of the solidify liquid suitable for calcium orthophosphate base bone cement.
The purpose of the invention is achieved by the following technical solution:
A kind of solidify liquid suitable for calcium orthophosphate base bone cement, including the following component being calculated by mass percentage:
The calcium orthophosphate base bone cement refers to the bone cement system containing calcium phosphate for principal component.
The citric acid is preferably the citric acid of medical grade.
The PVP is preferably the PVP of medical grade or food-grade；More preferably K value be 12~100 PVP；It is further excellent
It is selected as one of PVPK15, PVPK17, PVPK30, PVPK90 or at least two.
The phosphate is preferably one of sodium ascorbyl phosphate or potassium phosphate or at least two.
The phosphate is preferably one of sodium ascorbyl phosphate or at least two；The sodium ascorbyl phosphate includes phosphoric acid hydrogen
One of sodium, sodium dihydrogen phosphate, tertiary sodium phosphate or at least two.
The potassium phosphate includes one or both of potassium dihydrogen phosphate, dipotassium hydrogen phosphate.
The PVA is preferably the PVA of medical grade；More preferably alcoholysis degree is 86~99%, and average degree of polymerization (n) is
500~2500 PVA；Further preferably one of PVA05-88, PVA17-88, PVA-124 or at least two.
The water is preferably deionized water, distilled water or ultrapure water.
Solidify liquid of the invention is suitable for common calcium phosphate bone cement, and the calcium phosphate bone cement refers in this field
Usually used tricalcium phosphate system bone cement；Specially " calcium dihydrogen phosphate-type alpha tricalcium phosphate-calcium carbonate " system bone water
Mud, " tetracalcium phosphate-type alpha tricalcium phosphate " system bone cement, " tetracalcium phosphate-bata-tricalcium phosphate-calcium dihydrogen phosphate " system bone
Any one of cement, or " calcium monohydrogen phosphate-type alpha tricalcium phosphate-calcium carbonate " system bone cement.
The solidify liquid suitable for calcium orthophosphate base bone cement the preparation method comprises the following steps:
(1) citric acid for dissolving formula ratio, is prepared into solution A；
(2) phosphate that formula ratio is added into solution A, obtains solution B；
(3) PVP that formula ratio is added into solution B, obtains solution C；
(4) PVA of formula ratio is added into solution C, stirring dissolves PVA, cooling to be suitable for phosphorus for use to get described
The solidify liquid of sour calcium base bone cement.
Dissolution described in step (4) is preferably dissolved at 80 DEG C or more；Further preferably 30 are stirred at 80 DEG C
Minute is dissolved.
Described repairs the application medical material in bone injury suitable for the solidify liquid of calcium orthophosphate base bone cement.
The applicable solidify liquid of the calcium orthophosphate base bone cement is used in mixed way with common calcium phosphate bone cement, as bone injury
Repair medical material, application method are as follows: in the ratio of 0.4~0.9mL/g of liquid-solid ratio by the solidify liquid and the phosphorus
Sour calcium bone cement is uniformly mixed, and reconciles into paste, and paste is implanted directly into operative site by instrument and uses, and is carried out clinic and is answered
With.
For the present invention on the basis of common calcium phosphate bone cement, preparation is for solidification required for calcium phosphate bone cement solidification
Sodium ascorbyl phosphate is utilized to the promotion ability of early hydration product in liquid；The acidic environment of citric acid provides；PVP is to synthos
The numerator mediated effect of deposition；The water conservation sexual function of PVA dexterously makes each component of solidify liquid organically combine and mutually cooperate with,
Calcium phosphate bone cement ability to cure, early strength, later strength and its anti-blood punching performance are improved, calcium phosphate bone cement has been expanded
Medical value, while making the use standard of calcium phosphate bone cement more approach clinic.
The present invention has the following advantages and effects with respect to the prior art:
1, present invention utilizes the water-soluble characters of PVP, and in the case where solidifying the reduction of initial stage water phase, PVP will form small
Molecular structure；The incorporation of sodium ascorbyl phosphate at this time can effectively accelerate the deposition of synthos；Made using the collaboration of PVP and sodium ascorbyl phosphate
With increase nucleation site and the crystallization for accelerating calcium phosphate；Secondly the excellent compatibility and its water conservation between PVA and phosphate are utilized
Performance makes solidified body form an effective growing space, guarantees the growth of crystal, so as to improve good early strength；And it is ingenious
The early strength and later strength of bone cement matrix are realized by the synergistic effect of citric acid and sodium ascorbyl phosphate and PVP and PVA in ground
Raising.
2, it has been investigated that the solidify liquid containing citric acid, sodium ascorbyl phosphate, PVP, PVA, which is added, in the present invention is formed by phosphoric acid
Calcium bone cement does not change the voluntarily curing characteristics of raw calcium phosphate bone cement, and do not change solidify after hydrated product composition (its
Aquation composition is weak crystalline hydroxy apatite).
3, after tested, solidify liquid generates biggish raising to the setting time of calcium phosphate bone cement in the present invention.
4, after tested, solidify liquid generates biggish mention to the early stage of calcium phosphate bone cement and later period mechanical performance in the present invention
It is high.
5, medical material is repaired using the bone injury that solidify liquid of the invention and common calcium phosphate bone cement are prepared to have
There is more excellent biocompatible property, better clinical application effect can be obtained, had a good application prospect.
Detailed description of the invention
Fig. 1 is that the SEM of the bone cement obtained after calcium phosphate bone cement solid phase CPC-1 and solidify liquid L1 aquation schemes.
Fig. 2 is that the SEM of the bone cement obtained after calcium phosphate bone cement solid phase CPC-1 and solidify liquid L2 aquation schemes.
Fig. 3 is that the SEM of the bone cement obtained after calcium phosphate bone cement solid phase CPC-1 and solidify liquid L4 aquation schemes.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Associated materials involved in embodiment:
1. calcium dihydrogen phosphate used in embodiment, calcium monohydrogen phosphate, calcium carbonate, hydroxyapatite (HAP) are commercially available
Chemical pure raw material, and have passed through ball-milling treatment to partial size is 10~50 microns.
2. type alpha tricalcium phosphate (α-TCP)
Used type alpha tricalcium phosphate (α-TCP) is Solid phase synthesis, and the specific method is as follows: the preparation of α-TCP is using high
Warm calcination method, calcium carbonate (CaCO3) and calcium monohydrogen phosphate (CaHPO4·2H2O) with the mixing of calcium phosphorus molar ratio 1.5, according to powder and wine
The mass ratio of essence is that 1:2 is mixed with absolute alcohol, in the ball mill with the speed ball milling 30min of 200rpm, through centrifugation, drying,
The powder of sieving is placed in Muffle furnace after being calcined to 1350 DEG C, is taken out after sample heat preservation 4h, is chilled to room temperature in air.I.e.
α-TCP used in the embodiment of the present invention can be obtained.
3. tetracalcium phosphate
Tetracalcium phosphate used in embodiment is prepared via a method which to obtain:
According to the molar ratio 2.0 of calcium P elements, calcium carbonate and dicalcium phosphate dihydrate are weighed respectively；Row is poured into after being mixed
In celestial body grinding jar, using dehydrated alcohol as wet grinding media；It mills to dry after 4 hours and be put into crucible.Material liter after milling
Temperature is to 850 DEG C；Keep the temperature 30min；Continue to be warming up to 1200 DEG C；Keep the temperature 30min；1500 DEG C are finally warming up to, 2h is kept the temperature；It takes out simultaneously
It is chilled to room temperature, products therefrom is tetracalcium phosphate.
4. the preparation of solidify liquid
Solidify liquid used in embodiment is prepared via a method which to obtain:
(1) by the lemon acid dissolution of doses, it is prepared into solution A；
(2) a certain amount of sodium ascorbyl phosphate is added into A, obtains B；
(3) a certain amount of PVP is added into B, obtains C；
(4) a certain amount of PVA is added into C, and is stirred 30 minutes at 80 DEG C, and D is obtained；
(5) D is cooling stand-by.
The preparation of 1 calcium phosphate bone cement solid phase of embodiment and solidify liquid
1. the preparation of calcium phosphate bone cement solid phase
(1)CPC-1
Calcium dihydrogen phosphate-type alpha tricalcium phosphate-calcium carbonate pastern bone cement: by 3~10wt% of calcium dihydrogen phosphate, alpha-phosphate three
80~92wt% of calcium, 5~10wt% of calcium carbonate are uniformly mixed, and obtain calcium phosphate bone cement solid phase.
(2)CPC-2
By type alpha tricalcium phosphate (60~80wt%), tetracalcium phosphate (TECP) (20~30wt%) and hydroxyapatite (HAP)
(1~10wt%) is uniformly mixed, calcium phosphate bone cement solid phase.
2. the preparation of solidify liquid
By the formula (surplus is water) of table 1, the solidify liquid that number is L1~L10 is prepared respectively.
The formula of 1 solidify liquid of table
| It forms (wt%) | L1 | L2 | L3 | L4 | L5 | L6 | L7 | L8 | L9 | L10 |
| Citric acid | 0 | 4 | 3 | 2 | 2 | 3 | 2 | 3 | 3 | 2 |
| Na2HPO4 | 0 | 10 | 0 | 4 | 0 | 0 | 5 | 5 | 1 | 0 |
| NaH2PO4 | 0 | 1 | 15 | 15 | 20 | 0 | 5 | 3 | 0 | 2 |
| PVA05-88 | 0 | 0 | 4 | 3 | 4 | 3 | 3 | 0 | 3 | 0 |
| PVPK17 | 0 | 3 | 2 | 1 | 5 | 4 | 0 | 0 | 0 | 0 |
| Sodium alginate | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 2 | 0 |
| Chitosan | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 1 |
The detection of 2 physicochemical property of embodiment
The calcium phosphate bone cement that embodiment 1 is prepared is mixed with solidify liquid with liquid-solid ratio 0.5mL/g, is carried out after solidification
The detection of following physicochemical property.
1. curing time tests
The test of setting time is carried out according to U.S. material and experiment association criterion ASTM C190-03.Vicat apparatus pressure used
Nose heave 300 ± 0.5g, 1 ± 0.05mm of needle diameter.Testing procedure is as follows: sample is put into 37 DEG C after reconciling, the perseverance of 95% humidity
In constant temperature and humidity case, since start add solidify liquid when timing, loosen pressure head, test point freely sinks to slurry, when test point sink to it is small
When 25mm, reach initial set, when test point is when sample surfaces are without obvious impression, reaches final set, every 30s test is primary, each sample
Product are repeated 6 times, and calculate average value and standard deviation.
2. intensity test
CPC sample is respectively 6mm with diameter after reconciling, and the punching block (intensity test sample) and diameter of a height of 12mm is
The punching block (Radial drawing strength test sample) of 6mm, a height of 3mm forms, later immediately be directly the cylinder of 5.6mm with
700kPa's forces 5 seconds, and air pocket remaining in sample is discharged, sample is put into 37 DEG C later, and the constant temperature of 95% humidity is permanent
It is conserved in wet tank, conserves certain time rear demoulding, use the 5567 type electronic universal material of INSTRON of INSTRON company of the U.S.
Experimental machine comes the compression strength of test sample, loading speed 1mm/min.Each sample is repeated 6 times, and calculates average value and standard
Deviation.
By test, the solidify liquid tune that calcium phosphate bone cement solid phase and embodiment 1 are prepared by the component solutions of table 2
With it is rear, the comparison of the physicochemical property tested is as shown in table 2:
2 physicochemical property test result of table
Note: after " 10h " indicates that calcium phosphate bone cement solidifies ten hours；After " 3d " indicates that calcium phosphate bone cement solidifies three days.
2 result of analytical table is it is found that in tricalcium phosphate bone cement hydration process, if any additive is not added in solidify liquid,
Its curing time is long, and intensity is not high (2 serial number 1 of table)；The incorporation of sodium ascorbyl phosphate can effectively accelerate the deposition of synthos；
Improve the setting time (2 serial number 8 of table) of slurry；Influence of the content of PVP to bone cement is bigger, but needs with sodium ascorbyl phosphate
Collaboration promotes the effect (2 serial number 2~6 of table) of aquation using can just play, and PVP is used alone and can not play raising condensation
The purpose (2 serial number 6 of table) of time and intensity；But be single use sodium ascorbyl phosphate can improve setting time but its early strength with
Later strength is not high (2 serial number 8 of table)；The effect of PVA is to improve the later strength (2 serial number 7 of table) of solidified body.So passing through
The present embodiment can be seen that three and cooperate with using the hydration capability that will be helpful to improve tricalcium phosphate system bone cement, improve it
Operating characteristics.
And we also simply implement addition liquid additive (sodium alginate, chitosan) more common at present and do performance
Control, as the result is shown citric acid and sodium ascorbyl phosphate (coagulant) and sodium alginate (2 serial number 9 of table), chitosan (2 serial number 10 of table)
Cooperation can not achieve the effect that the solidify liquid prepared by us.In the present invention, we not only utilize citric acid and phosphoric acid
The rush of sodium salt condenses performance, it is often more important that is dexterously realized by the synergistic effect of citric acid and sodium ascorbyl phosphate and PVP and PVA
The raising of the early strength and later strength of bone cement matrix.
3 microscopic appearance phenetic analysis of embodiment
Using scanning electron microscope (Carl Zeiss company, Germany) to serial number 1 (group is divided into CPC-1+L1) in table 2,
The microscopic appearance carry out table of the bone cement obtained after serial number 2 (group is divided into CPC-1+L2), serial number 4 (group is divided into CPC-1+L4) aquation
Sign, as a result as shown in Figures 1 to 3.
Fig. 1 shows the solidify liquid that any additive is not added and the crystalline solid shape appearance figure after bone cement powder aquation, knot
Sheet is presented in crystalline form looks and size is micron or more.
Fig. 2 shows the microscopic appearance of CPC-1+L2 component bone cement, and compared to Figure 1 size is obviously inclined for crystallization shape
It is small；Reorganization solidify liquid has mainly used citric acid, sodium ascorbyl phosphate and its PVP, and citric acid and sodium ascorbyl phosphate mainly play promotion crystalline substance
The effect of body crystallization, PVP are wherein playing the role of refining grain size.Citric acid and PVP can act synergistically on knot simultaneously
The nucleation and growth of crystal, sodium ascorbyl phosphate is to the speed of growth and pattern for regulating and controlling crystal by way of ion doping；Pass through three
The synergistic effect of person can effectively improve setting time and its early anti pressured intension.The crystallite pattern that Fig. 2 is shown is to bone cement morning
Phase intensity has key effect.
Fig. 3 shows the microscopic appearance of CPC-1+L4 component bone cement.In the component, in addition to being added to citric acid, phosphoric acid
Sodium salt and its PVP also added reinforcing agent of the PVA as bone cement later strength.By the morphology analysis that Fig. 3 is shown:
Bone cement other than generating the microstructure that Fig. 2 is shown, yet forms the substance of many similar gluey connections after aquation,
Substance is contributed by PVA；Such structure can further strengthen the globality of bone cement matrix, to improve its later period resistance to compression
Intensity.
It is compared by the shape characteristic of Fig. 1~3, according to the specific bone cement macro property data of table 2: passing through lemon
The synergistic effect of acid, sodium ascorbyl phosphate, PVP and PVA, we realize effectively control calcium orthophosphate base bone cement setting time and its
Early, the later period mechanical performance regulation.
Influence of 4 acidic environment of embodiment to hydration behavior
In order to further study effect of the citric acid in the solidify liquid, the present embodiment is by citric acid and acetic acid and dilute hydrochloric acid
Comparative experimental study is carried out.
Citric acid in solidify liquid component L2 is specifically changed into the acetic acid (L2-C) and dilute hydrochloric acid (L2-CL) accordingly matched,
Other components are constant, studied by the test method of embodiment 2 its curing time and compression strength, as a result such as 3 institute of table
Show:
Table 3
As the result is shown: having certain promotion to setting time using acetic acid or dilute hydrochloric acid, but can be to bone cement matrix
Compression strength have a negative impact, research be considered the acid release due to acetic acid and dilute hydrochloric acid be it is disposable, cause solid
The habit for changing crystalline solid changes, so the reaction of its premature cure is caused to change, influences early stage and later strength.And this
The citric acid of invention not only promotes the setting time of bone cement, realizes rapid curing, while also significantly improving bone cement
The compression strength of matrix.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of solidify liquid suitable for calcium orthophosphate base bone cement, which is characterized in that be calculated by mass percentage including following
Component:
2. the solidify liquid according to claim 1 suitable for calcium orthophosphate base bone cement, it is characterised in that:
The citric acid is the citric acid of medical grade；
The PVP is the PVP of medical grade or food-grade；
The PVA is the PVA of medical grade；
The phosphate is one of sodium ascorbyl phosphate or potassium phosphate or at least two；
Surplus is water in the component of the solidify liquid.
3. the solidify liquid according to claim 1 suitable for calcium orthophosphate base bone cement, it is characterised in that:
The PVP is the PVP that K value is 12~100；
The PVA is that alcoholysis degree is 86~99%, the PVA that average degree of polymerization is 500~2500.
4. the solidify liquid according to claim 2 suitable for calcium orthophosphate base bone cement, it is characterised in that:
The PVP is one of PVPK15, PVPK17, PVPK30, PVPK90 or at least two；
The PVA is one of PVA05-88, PVA17-88, PVA-124 or at least two；
The phosphate is sodium ascorbyl phosphate.
5. the solidify liquid according to claim 2 suitable for calcium orthophosphate base bone cement, it is characterised in that:
The sodium ascorbyl phosphate includes one of dibastic sodium phosphate, sodium dihydrogen phosphate, tertiary sodium phosphate or at least two；
The potassium phosphate includes one or both of potassium dihydrogen phosphate, dipotassium hydrogen phosphate.
6. the solidify liquid according to claim 1 suitable for calcium orthophosphate base bone cement, it is characterised in that:
The calcium orthophosphate base bone cement is " calcium dihydrogen phosphate-type alpha tricalcium phosphate-calcium carbonate " system bone cement, " phosphoric acid four
Calcium-type alpha tricalcium phosphate " system bone cement, " tetracalcium phosphate-bata-tricalcium phosphate-calcium dihydrogen phosphate " system bone cement, or " phosphorus
Any one of sour hydrogen calcium-type alpha tricalcium phosphate-calcium carbonate " system bone cement.
7. the preparation method of the described in any item solidify liquids suitable for calcium orthophosphate base bone cement of claim 1~6, feature exist
In including the following steps:
(1) citric acid for dissolving formula ratio, is prepared into solution A；
(2) phosphate that formula ratio is added into solution A, obtains solution B；
(3) PVP that formula ratio is added into solution B, obtains solution C；
(4) PVA of formula ratio is added into solution C, stirring dissolves PVA, cooling to be suitable for calcium orthophosphate base bone to get described
The solidify liquid of cement.
8. the preparation method of the solidify liquid according to claim 7 suitable for calcium orthophosphate base bone cement, it is characterised in that:
It is dissolved as being dissolved at 80 DEG C or more described in step (4).
9. the described in any item solidify liquids suitable for calcium orthophosphate base bone cement of claim 1~6 repair medical material in bone injury
Application in material.
10. according to claim 9 repair medical material suitable for the solidify liquid of calcium orthophosphate base bone cement in bone injury
Application, which is characterized in that its application method are as follows:
In the ratio of 0.4~0.9mL/g of liquid-solid ratio by the described in any item solidify liquids of claim 1~6 and calcium phosphate bone cement
It is uniformly mixed, reconciles into paste, paste is implanted directly into operative site by instrument and uses, and carries out clinical application.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109939261A (en) * | 2019-04-24 | 2019-06-28 | 东南大学 | A kind of solidify liquid and its preparation method and application of controllable calcium phosphate bone cement injectivity |
| CN110665056A (en) * | 2019-09-23 | 2020-01-10 | 暨南大学 | Injectable bone cement with tissue self-bonding performance and preparation method and application thereof |
| CN112043862A (en) * | 2020-09-14 | 2020-12-08 | 香港大学深圳医院 | Magnesium slow-release bone cement with self-curing function and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01288269A (en) * | 1988-05-16 | 1989-11-20 | Tonen Corp | Composite molding |
| CN103965510A (en) * | 2013-01-29 | 2014-08-06 | 上海高科生物工程有限公司 | Bone cement capable of controllably releasing macromolecule proteins, and preparation method thereof |
| WO2015015212A1 (en) * | 2013-08-02 | 2015-02-05 | Ucl Business Plc | Formulations and materials with cationic polymers |
| CN104784752A (en) * | 2015-04-22 | 2015-07-22 | 山东明德生物医学工程有限公司 | Injectable bone cement with antioxidation characteristic as well as preparation method and application thereof |
| WO2018168474A1 (en) * | 2017-03-16 | 2018-09-20 | オリンパステルモバイオマテリアル株式会社 | Calcium phosphate cement composition, calcium phosphate cement kit, and method for producing cured calcium phosphate cement body |
-
2018
- 2018-10-18 CN CN201811215210.7A patent/CN109125804B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01288269A (en) * | 1988-05-16 | 1989-11-20 | Tonen Corp | Composite molding |
| CN103965510A (en) * | 2013-01-29 | 2014-08-06 | 上海高科生物工程有限公司 | Bone cement capable of controllably releasing macromolecule proteins, and preparation method thereof |
| WO2015015212A1 (en) * | 2013-08-02 | 2015-02-05 | Ucl Business Plc | Formulations and materials with cationic polymers |
| CN104784752A (en) * | 2015-04-22 | 2015-07-22 | 山东明德生物医学工程有限公司 | Injectable bone cement with antioxidation characteristic as well as preparation method and application thereof |
| WO2018168474A1 (en) * | 2017-03-16 | 2018-09-20 | オリンパステルモバイオマテリアル株式会社 | Calcium phosphate cement composition, calcium phosphate cement kit, and method for producing cured calcium phosphate cement body |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109939261A (en) * | 2019-04-24 | 2019-06-28 | 东南大学 | A kind of solidify liquid and its preparation method and application of controllable calcium phosphate bone cement injectivity |
| CN109939261B (en) * | 2019-04-24 | 2021-06-11 | 东南大学 | Curing liquid capable of regulating and controlling injection property of calcium phosphate bone cement and preparation method and application thereof |
| CN110665056A (en) * | 2019-09-23 | 2020-01-10 | 暨南大学 | Injectable bone cement with tissue self-bonding performance and preparation method and application thereof |
| CN110665056B (en) * | 2019-09-23 | 2022-01-11 | 暨南大学 | Injectable bone cement with tissue self-bonding performance and preparation method and application thereof |
| CN112043862A (en) * | 2020-09-14 | 2020-12-08 | 香港大学深圳医院 | Magnesium slow-release bone cement with self-curing function and preparation method thereof |
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| CN109125804B (en) | 2021-03-19 |
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