CN101352584B - Bone cement with biological decomposability and preparation method thereof - Google Patents
Bone cement with biological decomposability and preparation method thereof Download PDFInfo
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- CN101352584B CN101352584B CN 200710138463 CN200710138463A CN101352584B CN 101352584 B CN101352584 B CN 101352584B CN 200710138463 CN200710138463 CN 200710138463 CN 200710138463 A CN200710138463 A CN 200710138463A CN 101352584 B CN101352584 B CN 101352584B
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- 239000002639 bone cement Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 24
- GBNXLQPMFAUCOI-UHFFFAOYSA-H tetracalcium;oxygen(2-);diphosphate Chemical compound [O-2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GBNXLQPMFAUCOI-UHFFFAOYSA-H 0.000 claims description 44
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 33
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 18
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical class OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 15
- 239000001530 fumaric acid Substances 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 15
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 14
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 claims description 3
- 229940043256 calcium pyrophosphate Drugs 0.000 claims description 3
- 235000019821 dicalcium diphosphate Nutrition 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- 229920001299 polypropylene fumarate Polymers 0.000 abstract description 21
- LFULEKSKNZEWOE-UHFFFAOYSA-N propanil Chemical compound CCC(=O)NC1=CC=C(Cl)C(Cl)=C1 LFULEKSKNZEWOE-UHFFFAOYSA-N 0.000 abstract description 15
- 239000011575 calcium Substances 0.000 abstract description 9
- 230000037118 bone strength Effects 0.000 abstract description 4
- 230000005855 radiation Effects 0.000 abstract description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- ZLUFYQVHJAVDHU-IHWYPQMZSA-N (6z)-2-methyl-2,3-dihydro-1,4-dioxocine-5,8-dione Chemical compound CC1COC(=O)\C=C/C(=O)O1 ZLUFYQVHJAVDHU-IHWYPQMZSA-N 0.000 abstract 1
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- -1 poly propylene fumarate Polymers 0.000 abstract 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 11
- 239000004926 polymethyl methacrylate Substances 0.000 description 11
- 229920002521 macromolecule Polymers 0.000 description 10
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- 210000000459 calcaneus Anatomy 0.000 description 5
- 239000004568 cement Substances 0.000 description 5
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 5
- 229960001939 zinc chloride Drugs 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
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- 230000000694 effects Effects 0.000 description 4
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- 238000006703 hydration reaction Methods 0.000 description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 4
- 239000001506 calcium phosphate Substances 0.000 description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 description 3
- 235000011010 calcium phosphates Nutrition 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 206010041569 spinal fracture Diseases 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 238000000635 electron micrograph Methods 0.000 description 2
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- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
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- 206010010214 Compression fracture Diseases 0.000 description 1
- 108090000723 Insulin-Like Growth Factor I Proteins 0.000 description 1
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- 208000006193 Pulmonary infarction Diseases 0.000 description 1
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- 102000013275 Somatomedins Human genes 0.000 description 1
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- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
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Abstract
The invention relates to a bone cement with biological decomposability and a preparation method thereof. Macromolecular poly propylene fumarate (PPF) and the double-phase material of tracalcium phosphate (TTCP)/anhydrous calcium hydrophosphate (DCPA) are mixed to derive the bone cement material with biological decomposability. The bone cement material derived by the preparation method of the invention has the advantages of syringeability, biological decomposability, radiation imperviousness, compressive strength closer to bone strength, lower polymeric temperature, high biological compatibility, etc.
Description
[technical field]
The invention provides a kind of bone cement with Biodegradable and preparation method thereof, refer to especially a kind of with a polyphosphazene polymer fumaric acid two hydroxypropyl acrylates (poly (propylene fumarate), be called for short PPF) and a tetracalcium phosphate (Tetracalcium phosphate, Ca
4O (PO)
2, be called for short TTCP)/calcium phosphate dibasic anhydrous (Dicalcium phosphateanhydrous, CaHPO
4, be called for short DCPA) binary phase materials mix and use, with the bone cement material as the damaged filling of skeleton, and relevant preparation method.
[background technology]
Rising along with the social life level, the progress of medical treatment, it has been predictable that population steps into aging, and is accompanied by the disease that aging produces, as: osteoporosis and the complication that is derived thereof more become key subjects that affect the senior health and fitness.The modal complication of osteoporosis is exactly the vertebra compression fracture, because the osteoporosis meeting is so that the fragile danger that increases fracture of bone, in the U.S., namely there are 700,000 every year because the spinal fracture case that osteoporosis causes approximately has 100,000 cases thereby needs hospitalization.
In recent years, spine orthopedic art (vertebroplasty) begins to be used in the repressive spinal fracture for the treatment of aspect.The principle of spine orthopedic art exactly bone cement is squeezed into fracture site go firm it, reach the effect that relieves pain.
Be applied at present bone cement on the spine orthopedic art mostly take PMMA as main, because bone cement PMMA can provide enough intensity in the early stage the time, but it still has following many shortcomings to overcome:
One, the caused pyroreaction of polymerization will cause sensory nerve ending to be burnt out by high temperature.
Two, residual liquid: MMA is the virose material of tool, in case leak outside, might cause the Venous system obstruction, and then cause pulmonary infarction.
Three, compared to natural bone tissue, the intensity after the bone cement PMMA sclerosis is excessive, might cause stress concentration, so that produce secondary osteoporosis and fracture.
Four, the abiotic degradable materials of bone cement PMMA can hinder the carrying out of bone remodeling; Leak outside if produce in the operation, may need second operation to remove.
Five, can't there be direct bond to produce by the calcaneus head.
Aforementioned shortcoming, many people attempt to add some materials and go to improve its character, as: add ceramic particle, demineralized bone (DBM), to increase its biological activity, cross the problems such as high with reducing intensity, only, effect all is not very good.
Except bone cement PMMA, popular bone cement is the bone cement of pottery series in the recent period, as: calcium phosphate cement (CPC), this class cement has following many advantages compared with bone cement PMMA:
One, the bio-compatibility of calcium phosphate cement (CPC) is high, all is synthos basically because its structure calcaneus is organized, and therefore can directly produce bond by the calcaneus head.
Two, because its structure calcaneus is organized identically, can participate in reinventing of bone directly, not need removing of second operation, utilize this character, can in cement, add some somatomedin, promote the reparation of skeleton to follow and reinvent.
Three, because its intensity near bone strength, can not damaged other bone etc. by pressure.
Only, aforementioned calcium phosphate cement (CPC) can't reach requirement clinically because the insufficient strength at initial stage is strong.This shows, can significantly promote spine orthopedic art treatment vertebral bone discharging the retained water effect if can improve known bone cement or develop a kind of new bone cement.
[summary of the invention]
Because at present for spinal fracture that osteoporosis the caused good and perfect solution of neither one still, spine orthopedic art (vertebroplasty) because of the shortcoming of known bone cement, is not subjected to doctor's favor in the use always; Therefore, the inventor is through permanent effort research and experiment according to the correlation experience of being engaged in for many years in this respect, and cooperates relevant scientific principle, and development and Design goes out a kind of " having bone cement of Biodegradable and preparation method thereof " of the present invention finally.
The present invention's main purpose, be to provide a kind of bone cement with Biodegradable and preparation method thereof, after it ties up to and prepares polyphosphazene polymer fumaric acid two hydroxypropyl acrylates (PPF), it is dissolved in the NVP (N-VP) stirs, again a tetracalcium phosphate (TTCP)/calcium phosphate dibasic anhydrous (DCPA) is dissolved in the N-VP/PPF solution, in a baking powder (BP) pass into solution, again with both mix homogeneously, at room temperature allow its completion of cure, to obtain the present invention's the bone cement with Biodegradable.This bone cement not only has novelty, and have more progressive and practicality, can inject fracture, have Biodegradable by injection system such as: this bone cement, and the temperature when better engineering properties, polymerization are arranged is lower than known bone cement PMMA, than known bone cement PMMA more near the comprcssive strength of bone strength, have high bio-compatibility, have the lonizing radiation impervioursness, therefore have very large practicality for the application in the spine orthopedic art.
[description of drawings]
It is qualitative that Fig. 1 is that the present invention's tetracalcium phosphate (TTCP) goes material with X-ray diffraction analysis instrument, via JCPDS data base's standard diagram comparison schematic diagram.
Fig. 2 is that the present invention's the end-product calcium deficiency oxyhydrogen-base apatite (dHAP) for after tetracalcium phosphate (TTCP)/calcium phosphate dibasic anhydrous (DCPA) hydration is qualitative to material with X-ray diffraction analysis instrument, via JCPDS data base's standard diagram comparison schematic diagram.
Fig. 3 is the electron micrograph of the present invention's bone cement material surface.
[specific embodiment]
Your juror can further understanding and understanding be arranged to the present invention's technological means and operation for ease of, hereby to cooperate graphicly for an embodiment, be described in detail as follows.
The present invention is a kind of bone cement with Biodegradable and preparation method thereof, it is with a polyphosphazene polymer fumaric acid two hydroxypropyl acrylates (poly (propylene fumarate), be called for short PPF) and a tetracalcium phosphate (Tetracalciumphosphate, Ca
4O (PO)
2, be called for short TTCP)/calcium phosphate dibasic anhydrous (Dicalcium phosphate anhydrous, CaHPO
4, be called for short DCPA) binary phase materials mix and use, use obtaining a bone cement material with Biodegradable; Because these polyphosphazene polymer fumaric acid two hydroxypropyl acrylates (PPF) have oligomerization temperature, biodegradability, can be used as the injected bone cement applications, and can form porous structure after this tetracalcium phosphate (TTCP)/calcium phosphate dibasic anhydrous (DCPA) is fixed, and the structure calcaneus is organized close, has quite high bio-compatibility, can participate in the process that bone is rebuild directly, therefore the present invention be with aforementioned both be mixed, with the usefulness as the skeleton filling.
Below be the embodiment of macromolecule PPF preparation method in the bone cement material of the present invention:
It is the reaction preparation via two steps, adopt pyrocinchonic acid (Dimethyl Fumarate, vehicle economy F), propylene glycol (Propylene Glycol, be called for short PG) be main material, adding zinc chloride (zinc chloride is called for short ZnCl2) is used as catalyst and hydroquinone (hydroquinone is called for short Hq) and is used as cross-linked inhibitor and synthesizes desired macromolecule PPF.
First step is got mole than pyrocinchonic acid (DEF): propylene glycol (PG): zinc chloride (ZnCl
2): hydroquinone (Hq)=1: 3: 0.01: 0.002 carries out uniform stirring, and temperature is raised to 100 ℃, then slowly is heated to 150 ℃, and course of reaction must be carried out under the state of secluding air, so logical nitrogen.In the course of reaction, pyrocinchonic acid (DEF) can produce ethanol with propylene glycol (PG) reaction, utilizes condensing tube that its condensation is got off, when ethanol not when condensing, the reaction of expression first step is finished;
Second step, Temperature Setting at 100 ℃, is evacuated to 0.1 Bristol (Torr) with pressure, in this process, unreacted propylene glycol (PG) will be condensed out, in two hours temperature is risen to 130-150 ℃ afterwards, begin to be reacted into macromolecule PPF this moment, at two hours temperature is increased to 200 ℃, and 200 ℃ of constant temperature 12 hours, being cooled to afterwards room temperature, producing the amber color liquid with vicidity, is exactly desired product macromolecule PPF.
Because the macromolecule PPF for preparing contains catalyst (zinc chloride) in the inside, cross-linked inhibitor (hydroquinone) does not remove, so need purification to be removed, its purification step is: macromolecule PPF is dissolved in the dichloromethane with volume one the ratio of making a comparison, add again the hydrogen chloride that concentration is 1N (HCl) and remove catalyst (zincchloride), afterwards again with the intermediate water of equal volume, saline extracts repeatedly, to remove organic solvent dichloromethane, add afterwards concentrated sulphuric acid and remove unnecessary moisture, again remaining macromolecule PPF and dichloromethane solution are added cold ether, to get rid of unnecessary cross-linked inhibitor (hydroquinone), roughly purification is complete through this step macromolecule PPF, but because dichloromethane is toxic organic solvent, so at last the product utilization vacuum drying is removed unnecessary organic solvent, macromolecule PPF behind the purification should be stored under-20 ℃ when not using.
Take next in the bone cement material of the present invention the embodiment of tetracalcium phosphate (TTCP)/calcium phosphate dibasic anhydrous (DCPA) preparation method:
First step is got a mole calcium pyrophosphate (Ca according to stoichiometric proportion
2P
2O
7) powder and two mole calcium carbonate (CaCO
3) powder, make its abundant mix homogeneously after, even mixture is tiled in the platinum pincers pot, place carborundum (SiC) high temperature furnace to carry out high temperature sintering;
Second step, with the 10 ℃/rate of heat addition of minute (min), the temperature that is heated to sintering is 1440 ℃, and holds temperature three hours in this temperature with this mixture of powders, afterwards must Xun Su temper fire to room temperature, so, namely obtain tetracalcium phosphate (TTCP); In the present embodiment, be to grind to form fine powder with mortar, use again dusting cover (screen cloth model mesh No.106) to filter, its reaction equation is as follows:
Ca
2P
2O
7+2CaCO
3→Ca
4(PO
4)
2O+2CO
2；
Third step, with the above-mentioned tetracalcium phosphate that obtains (TTCP) powder and a calcium phosphate dibasic anhydrous (DCPA) with the ratio mix homogeneously of a mole than a mole after, namely obtain tetracalcium phosphate (TTCP)/calcium phosphate dibasic anhydrous (DCPA) two-phase bone cement.
In addition, curing mechanism about tetracalcium phosphate (TTCP)/calcium phosphate dibasic anhydrous (DCPA) two-phase bone cement, react because tetracalcium phosphate (TTCP) and calcium phosphate dibasic anhydrous (DCPA) are easily and waterishlogging is living, the initial stage hydration can form oxyhydrogen-base apatite, then form oxyhydrogen-base apatite (the Calcium-deficient hydroxyapatite of calcium deficiency thereafter, be called for short dHAP), and these some calcium deficiency oxyhydrogen-base apatites (dHAP) can form acicular texture, these acicular textures can be used as a nucleus with HAP, long brilliant the higher authorities, be staggered to form each other the result that stable structure reaches material cured, its reaction equation is as follows:
Initial reaction:
2Ca
4(PO
4)
2O+2CaHPO
4+H
2O→Ca
10(PO
4)(OH)
2
Late phase reaction:
2Ca
4(PO
4)
2O+2CaHPO
4+H
2O→Ca
10-X(HPO
4)
X(PO
4)
6-X(OH)
2-X，0≤X≤1
See also shown in Figure 1, system is after tetracalcium phosphate (TTCP) prepares, and we go material qualitative with X-ray diffraction analysis instrument, via the schematic diagram of JCPDS data base's standard diagram comparison, find out by knowing among the figure, prepared material crest all has identical with standard diagram; And the essential condition of X-ray winding is: between atomic layer the interval must be identical with radiation wavelength, and the scattering environments of scattering center must have the height systematicness, with the specific peak of the diffraction that utilizes material, namely can do qualitative to the crystalline phase of material.
See also shown in Figure 2, X-ray diffraction analysis instrument collection of illustrative plates for the end-product calcium deficiency oxyhydrogen-base apatite (dHAP) after tetracalcium phosphate (TTCP)/calcium phosphate dibasic anhydrous (DCPA) hydration, by collection of illustrative plates as can be known, end-product is the calcium deficiency oxyhydrogen-base apatite (dHAP) similar with human body mineralising bone component really after the hydration.
Mat the above, after finishing respectively the macromolecule PPF and tetracalcium phosphate (TTCP)/calcium phosphate dibasic anhydrous (DCPA) for preparing, can be mixed with according to the following step:
At first, polyphosphazene polymer fumaric acid two hydroxypropyl acrylates (PPF) are dissolved in the NVP (N-vinylpyrrolidone, be called for short N-VP) stir;
Secondly, tetracalcium phosphate (TTCP)/calcium phosphate dibasic anhydrous (DCPA) is dissolved in the N-VP/PPF solution;
Afterwards baking powder (Baking Powder, abbreviation BP) in the pass into solution, again with both mix homogeneously, pour in the mould, at room temperature allow its completion of cure, namely making the bone cement with Biodegradable of what is called of the present invention, see also shown in Figure 3ly, is the electron micrograph of bone cement material surface.
In sum, the bone cement material of prepared polyphosphazene polymer fumaric acid two hydroxypropyl acrylates (PPF) out of the present invention and tetracalcium phosphate (TTCP)/calcium phosphate dibasic anhydrous (DCPA), not only have novelty, and have more with purgation progressive and practicality:
One, can inject fracture by injection system.
Two, have Biodegradable, and better engineering properties is arranged.
Three, the temperature during polymerization is lower than known bone cement PMMA.
Four, than known bone cement PMMA more near the comprcssive strength of bone strength.
Five, has high bio-compatibility.
Six, has lonizing radiation impervioursness (do not need to add developing agent, the better development effect than known bone cement PMMA is namely arranged, avoid adding developing agent barium sulfate).
Seven, has very large practicality for the application in the spine orthopedic art.
Therefore, above-mentioned detailed description is for a kind of preferred embodiment explanation of the present invention, this embodiment be not limit the present invention apply for a patent the model horse stable, such as other does not break away from lower equalization of finishing of disclosed skill spirit and changes and modify change, all should be included in the claim that the present invention contains.
Claims (8)
1. bone cement preparation method with Biodegradable, this preparation method comprises:
A. adopt pyrocinchonic acid, catalyst is used as by propylene glycol, interpolation zinc chloride and hydroquinone is used as poly-fumaric acid two hydroxypropyl acrylates of cross-linked inhibitor synthetic high polymer;
B. polyphosphazene polymer fumaric acid two hydroxypropyl acrylates are dissolved in the NVP and stir;
C. tetracalcium phosphate/calcium phosphate dibasic anhydrous is dissolved in NVP/polyphosphazene polymer fumaric acid two hydroxypropyl acrylate solution; And
D. in the baking powder pass into solution, again with both mix homogeneously, at room temperature allow its completion of cure, form the bone cement with Biodegradable.
2. the bone cement preparation method with Biodegradable according to claim 1, the preparation method of these polyphosphazene polymer fumaric acid two hydroxypropyl acrylates wherein comprises:
A1. get the mol ratio pyrocinchonic acid: propylene glycol: zinc chloride: hydroquinone=1: 3: 0.01: 0.002 carries out uniform stirring;
A2. temperature is raised to 100 ℃, then slowly is heated to 150 ℃, course of reaction is carried out under the state of secluding air; With Temperature Setting at 100 ℃, pressure is evacuated to 0.1 Bristol, in two hours, temperature is risen to 130-150 ℃ afterwards, in two hours, temperature is increased to 200 ℃, and 200 ℃ of constant temperature 12 hours, being cooled to afterwards room temperature, producing the amber color liquid with vicidity, is exactly desired product polyphosphazene polymer fumaric acid two hydroxypropyl acrylates.
3. the bone cement preparation method with Biodegradable according to claim 2, wherein these polyphosphazene polymer fumaric acid two hydroxypropyl acrylates need be removed catalyst, the cross-linked inhibitor that the inside is contained by purification, and its purification step is:
B1. polyphosphazene polymer fumaric acid two hydroxypropyl acrylates are dissolved in the dichloromethane with volume one the ratio of making a comparison, add again hydrogen chloride and remove catalyst;
B2. intermediate water, the saline with equal volume extracts repeatedly, removes organic solvent dichloromethane, adds afterwards concentrated sulphuric acid and removes unnecessary moisture;
B3. more remaining polyphosphazene polymer fumaric acid two hydroxypropyl acrylates and dichloromethane solution are added cold ether, to get rid of unnecessary cross-linked inhibitor; And
B4. the product utilization vacuum drying is removed unnecessary organic solvent.
4. the bone cement preparation method with Biodegradable according to claim 1, the preparation method of this tetracalcium phosphate/calcium phosphate dibasic anhydrous wherein comprises:
C1., mixture of powders is provided, and this mixture of powders system is comprised of calcium pyrophosphate powder and calcium carbonate powder;
C2. this mixture of powders is carried out heat treated, obtain the tetracalcium phosphate powder; And
C3. tetracalcium phosphate powder and calcium phosphate dibasic anhydrous are mixed in proportion, obtain tetracalcium phosphate/calcium phosphate dibasic anhydrous.
5. the bone cement preparation method with Biodegradable according to claim 4, wherein the heat treated of this mixture of powders is the rate of heat addition with 10 ℃/minutes, the temperature that is heated to sintering is 1440 ℃, and sintering time was quenched under the room temperature after three hours, obtained tetracalcium phosphate.
6. the bone cement preparation method with Biodegradable according to claim 4, wherein this mixture of powders system is tiled in the platinum crucible, places the carborundum high temperature furnace to carry out high temperature sintering.
7. bone cement with Biodegradable, it is the bone cement material that is mixed by polyphosphazene polymer fumaric acid two hydroxypropyl acrylates and tetracalcium phosphate/calcium phosphate dibasic anhydrous.
8. the bone cement with Biodegradable according to claim 7, wherein this tetracalcium phosphate is synthesized by raw material take calcium pyrophosphate and calcium carbonate.
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| CN107137771B (en) * | 2017-05-02 | 2020-02-07 | 南京医科大学附属口腔医院 | Nano calcium phosphate bone cement and preparation method thereof |
| CN111973797B (en) * | 2020-09-04 | 2022-06-03 | 湖南奥星生物医药股份有限公司 | Non-invasive implantation high-viscosity adhesive material for orthopedics department and preparation method and application thereof |
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| US10183477B2 (en) | 2010-08-20 | 2019-01-22 | H. David Dean | Absorbant and reflecting biocompatible dyes for highly accurate medical implants |
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