CN114984328B - Composite bone repair material and preparation method thereof - Google Patents
Composite bone repair material and preparation method thereof Download PDFInfo
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- CN114984328B CN114984328B CN202210746255.7A CN202210746255A CN114984328B CN 114984328 B CN114984328 B CN 114984328B CN 202210746255 A CN202210746255 A CN 202210746255A CN 114984328 B CN114984328 B CN 114984328B
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- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 77
- 230000008439 repair process Effects 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 29
- 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 claims abstract description 29
- CVPJXKJISAFJDU-UHFFFAOYSA-A nonacalcium;magnesium;hydrogen phosphate;iron(2+);hexaphosphate Chemical compound [Mg+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Fe+2].OP([O-])([O-])=O.OP([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O CVPJXKJISAFJDU-UHFFFAOYSA-A 0.000 claims abstract description 28
- 229910052591 whitlockite Inorganic materials 0.000 claims abstract description 28
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 20
- 239000004359 castor oil Substances 0.000 claims abstract description 20
- 235000019438 castor oil Nutrition 0.000 claims abstract description 20
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 20
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000004814 polyurethane Substances 0.000 claims abstract description 13
- 229920002635 polyurethane Polymers 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000005187 foaming Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000004970 Chain extender Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 238000009388 chemical precipitation Methods 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 3
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 230000004071 biological effect Effects 0.000 abstract description 2
- 230000008512 biological response Effects 0.000 abstract description 2
- 230000011164 ossification Effects 0.000 abstract description 2
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000011148 porous material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 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
- A61L27/56—Porous materials, e.g. foams or sponges
-
- 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
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than 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
- A61L27/50—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
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- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/16—Materials with shape-memory or superelastic properties
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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Abstract
The invention discloses a composite bone repair material and a preparation method thereof, wherein an organic component adopts castor oil to react with isophorone diisocyanate to synthesize polyurethane, an inorganic component comprises hydroxyapatite and whitlockite, and the organic component and the inorganic component are compounded in situ to obtain the bone repair material; in addition, the raw materials selected by the invention all take the biological activity and the biocompatibility into consideration, so that ideal biological response is achieved, and a good osteogenesis effect is obtained.
Description
Technical Field
The invention relates to the field of biomedical materials, in particular to a composite bone repair material and a preparation method thereof.
Background
Natural bone tissue is the hardest connective tissue of the human body, and skillfully combines organic bone matrix and inorganic bone salt in a very complicated way. Of all calcium phosphates, hydroxyapatite is most abundant in human bone. Due to its good biocompatibility, bioactivity and osteoconductivity, hydroxyapatite has been widely used in bone repair materials. However, the brittleness of hydroxyapatite limits its use in load bearing applications. In order to make up for the defect of poor mechanical properties, hydroxyapatite and polymers are generally compounded to prepare the artificial bone repair material.
In the prior art, the bone repair materials pay attention to performance parameters in two aspects of porosity and mechanical strength, and the resilience performance of the bone repair materials is not paid attention to, for example, the bone repair materials are CN106620870A, and the patent name is a method for preparing an antibacterial porous composite bone repair scaffold by a homogeneous self-foaming method, wherein the method comprises the steps of firstly preparing an nHA/DCPD/PU composite material, and then enabling the DCPD to release crystal water to react with isocyanate in a polyurethane prepolymer to generate CO at the temperature of more than 75℃ to generate CO 2 (ii) a Under the protection of nitrogen, 15g of glycerin-modified castor oil is added into a three-necked bottle, heated in oil bath at 70 ℃ and mechanically stirred for 0.5h, and 6.5g of DCPD solid powder and 65gnHA powder are added; gradually dropwise adding 15g of IPDI to obtain a composite material prepolymer; and then adding 0.05mL of catalyst, reacting for about 0.5h, adding 0.5mL of chain extender, continuing to react for 2h, curing and foaming at 90 ℃ for 24h, washing and drying to obtain the antibacterial porous composite bone repair scaffold, wherein the bone repair material prepared by the preparation method has good porosity and mechanical strength.
The patent No. CN104368041A, the patent name is the preparation method of the composite bone repair bracket with the oriented channel structure, the preparation method discloses that after a viscous calcium phosphate-polyurethane composite material is made into a film with the thickness of 0.02-3 mm, preferably 1-2 mm, metal wires with the diameter suitable for the required channel diameter are arranged on the surface of the composite bone repair bracket at intervals and are curled into a columnar solid, the composite bone repair bracket is cured for 1-48 hours, preferably 2-12 hours, under the condition of 90-120 ℃ (the maximum allowable range is 75-150 ℃, preferably 90-120 ℃), and then the metal wires are removed in an electrolyte containing electrolyte components in an electrolytic mode with the metal wires arranged in each orientation as an anode and an inert electrode as a cathode, so that the composite bone repair bracket with the oriented channel structure is obtained, and the porosity of the composite bone repair bracket is good.
However, human bones not only have requirements on porosity and mechanical strength, but also have requirements on resilience of bones at different parts of the human body, but the existing bone materials are not prepared with attention to the problem in the direction.
Disclosure of Invention
Therefore, in order to simultaneously improve the porosity, the mechanical property and the resilience of the bone repair material in the prior art and prepare the bone repair material which is closer to the human bone, the invention provides a composite bone repair material and a preparation method thereof.
In one aspect, the present invention provides a composite bone repair material,
the composite bone repair material comprises: the organic component adopts castor oil and isophorone diisocyanate to react to synthesize polyurethane, the inorganic component comprises hydroxyapatite and whitlockite, and the organic component and the inorganic component are compounded in situ to obtain the bone repair material.
The design idea of the composite bone repair material is to simulate bone tissues based on three aspects of components, structures and functions, and construct a novel bone repair body with bone induction activity and bone conduction activity through bidirectional regulation.
The inorganic component of the bone repair material is selected from hydroxyapatite and whitlockite, because the hydroxyapatite is the main inorganic component forming human skeleton in all calcium phosphates, the hydroxyapatite has good biocompatibility, bioactivity and bone conduction activity, and the hydroxyapatite is widely applied to the bone repair material. The whitlockite is a calcium phosphate derivative taking magnesium ions as second cations, has the content in human bones only second to that of hydroxyapatite, and has the advantages of high ion release speed, strong protein adsorption capacity, good stability in an acid environment and better bone induction activity.
Further, the whitlockite is prepared by reacting calcium hydroxide with magnesium hydroxide, dripping phosphoric acid into the solution after the reaction, and precipitating, centrifuging, washing and freeze-drying to obtain whitlockite powder; the hydroxyapatite is prepared by taking calcium nitrate and trisodium phosphate as raw materials through a chemical precipitation method.
Therefore, in order to be closer to the components of human bones, the research team of the invention firstly fixes the proportion of the castor oil to the isophorone diisocyanate to be 1, after the organic component polyurethane is prepared, the inorganic component is singly selected to use the whitlockite, and experimental research is respectively carried out on the inorganic component by the percentage content of 0%,5%,15%,25%,35%,45%,55% and 65%, and the result shows that when the inorganic component is 65% of the whitlockite, the prepared composite bone repair material has the optimal performance, the porosity can reach 66 +/-2%, the compressive strength can reach 5.2MPa, the resilience can reach 88%, and the performance is better compared with other percentage contents.
After the bone material is prepared by using one inorganic component alone, furthermore, the research personnel of the invention observe the performance of the prepared bone material by fixing the mass ratio of the castor oil to the isophorone diisocyanate to be 1 and the whole proportion of the inorganic component to be 65%, and adding the hydroxyapatite into the inorganic component gradually, and respectively carry out parallel experiments on different mass ratios of the hydroxyapatite and the whitlockite, and the results show that when the mass ratio of the hydroxyapatite to the whitlockite is 3.
Secondly, in the selection of the organic components, because the polyurethane is a block polymer consisting of soft segments and hard segments, the polyurethane can be designed by selecting different soft segment blocks and adjusting the proportion of the soft segments and the hard segments, so that polymers with different chemical structures, mechanical properties and thermal properties can be obtained to adapt to different application requirements, therefore, in order to synthesize a bone material with good performance, the castor oil and isophorone diisocyanate are adopted to react to synthesize the polyurethane, and the mass ratio of the castor oil to the isophorone diisocyanate is 1.
In another aspect of the present invention,
the preparation method of the composite bone repair material comprises a reaction section and a foaming section, wherein the reaction section and the foaming section are in continuous reaction;
a reaction section: adding reaction raw materials into a reactor in sequence: uniformly mixing hydroxyapatite, whitlockite and castor oil, and then adding isophorone diisocyanate, a catalyst and a chain extender; the reaction section was carried out in an oil bath with stirring.
A foaming section: and adding a foaming agent into the reaction section, uniformly stirring, discharging, and putting into an oven to prepare the composite bone repair material.
Further, the catalyst is stannous octoate, the chain extender is 1, 4-butanediol, and the foaming agent is water; in terms of dosage, the usage amount of the catalyst is 0.1-0.3% of the mass of the reaction raw material, the chain extender is 2-3% of the mass of the reaction raw material, and the water is 0.5-1% of the mass of the reaction raw material; the mass of the reaction raw materials is the sum of the mass of hydroxyapatite, whitlockite, castor oil, isophorone diisocyanate, a catalyst and a chain extender.
Furthermore, the temperature of the reaction section is selected to be 60-80 ℃, preferably 70 ℃, and the reaction time is 3-6h.
Furthermore, due to the influence of the whitlockite, the foaming temperature is not high, the foaming temperature is high, and the foaming collapses and the pore structure is influenced, so that the temperature of the foaming section is 60-80 ℃, and the foaming time is 12-24h.
Advantageous effects
The castor oil and the isophorone diisocyanate are selected to synthesize polyurethane, and the hydroxyapatite and the whitlockite are further compounded to prepare the bone repair material with the three-dimensional pore structure, so that the porosity can reach 75%, the compressive strength can reach 15MPa, the resilience rate is about 80%, the utilization rate of renewable resources is improved, the cost is reduced, and the selected raw materials all consider the biological activity and the biological compatibility, so that the ideal biological response is achieved, and a good bone formation effect is obtained.
Drawings
FIG. 1 is a photomicrograph of a bone repair material made in example 3.3;
FIG. 2 is a scanning electron microscope image of HA/WH/PU composite stent, wherein
FIGS. 2A and 2B are SEM pictures of the bone repair material of example 3.2;
FIGS. 2C and 2D are SEM pictures of the bone repair material of example 3.3;
in fig. 3, A1 is a photograph of the bone repair material sample of example 3.3 taken from the original height measurement, A2 is a photograph of the instantaneous height measurement after 4 cycles of compression are completed, and A3 is a photograph of the height measurement after 1 hour of recovery from the completion of the cycles of compression;
fig. 4 is a photomicrograph of the bone repair material prepared in example 4.2.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
Example 1
Fig. 1 is a picture of a bone repair material, and this example describes a method for preparing a bone repair material, in which an organic component is polyurethane synthesized by a reaction between castor oil and isophorone diisocyanate, an inorganic component includes hydroxyapatite and whitlockite, and the organic component and the inorganic component are in-situ compounded to obtain the bone repair material.
Specifically, the whitlockite in the inorganic component is prepared by reacting calcium hydroxide and magnesium hydroxide, wherein the ratio of anions to cations is 1, the ratio of calcium to magnesium in the cations is 37, mechanically stirring the materials, the temperature of a reaction water bath is 80 ℃, and after fully reacting for 1h, dropwise adding diluted phosphoric acid into the solution at the speed of 12.5 ml/min. Stopping stirring after the dropwise addition of the phosphoric acid solution is finished, precipitating in a water bath at the temperature of 80 ℃ for 6 hours, centrifuging, washing for 2-3 times, and placing in a freeze dryer for more than 48 hours to obtain the whitlockite powder.
The hydroxyapatite in the inorganic component is prepared by taking calcium nitrate and trisodium phosphate as raw materials and adopting a chemical precipitation method; the ratio of hydroxyapatite to whitlockite is 3.
The organic component is prepared by mixing castor oil and isophorone diisocyanate according to the ratio of 1.
The preparation process of the bone repair material comprises the following steps: the whole reaction was carried out in a 70 ℃ oil bath, and the electric stirrer was turned on and kept at a constant rotational speed. 19.5g of hydroxyapatite, 6.5g of whitlockite and 20g of castor oil are added in sequence, and after being stirred uniformly, 20g of isophorone diisocyanate is added dropwise. After the dropwise addition, the mixture is fully stirred for ten minutes, and 0.1mL of catalyst stannous octoate is dropwise added. Continuously stirring for reacting for about four hours, adding 2.5ml of chain extender 1, 4-butanediol, adding 0.8ml of water as a foaming agent after about one hour, fully stirring for 1-2min, and discharging. And after discharging, placing the sample in an oven at 60 ℃ for foaming for 24 hours to prepare the bone repair material.
Example 2
The bone repair material of this example was prepared in the same manner as in example 1, the ratio of the fixed castor oil to the isophorone diisocyanate was 1 in the absence of the added hydroxyapatite component, and the compressive strength, porosity, and resilience of the prepared composite bone repair material were compared by changing the percentage of the inorganic component, whitlockite, and the specific reaction results are shown in table 1.
TABLE 1
As can be seen from Table 1, with the increase of the content of the inorganic component whitlockite, the compressive strength of the prepared bone repair material gradually decreases and then gradually increases, which means that the content of the whitlockite influences the compressive strength of the bone material to a certain extent, and when the content reaches 65%, the porosity of the prepared bone repair material can reach 66 +/-2%, the compressive strength reaches 5.2MPa, and the resilience rate reaches 88% which is the highest.
Example 3
The process of this example is the same as example 1, the ratio of the fixed castor oil to the isophorone diisocyanate is 1, the inorganic components with different components are adopted, and the compressive strength, the porosity and the resilience of the prepared composite bone repair material are compared, and the specific conditions are shown in table 2.
TABLE 2
It can be seen from table 2 that, when hydroxyapatite and whitlockite are mixed, as the content of hydroxyapatite increases, at 3.
Example 4
The procedure of this example is the same as example 1, the content of the fixed inorganic component is 65%, different proportions of castor oil and isophorone diisocyanate are used to synthesize polyurethane, and the compressive strength, porosity and resilience of the prepared composite bone repair material are compared, and the specific conditions are shown in table 3.
TABLE 3
As can be seen from table 3 and fig. 4, when the ratio of castor oil to isophorone diisocyanate is 1.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The composite bone repair material is characterized in that organic components adopt castor oil to react with isophorone diisocyanate to synthesize polyurethane, inorganic components comprise hydroxyapatite and whitlockite, and the organic components and the inorganic components are compounded in situ to obtain the bone repair material; the content of the inorganic component is 15-65%, and the mass ratio of the castor oil to the isophorone diisocyanate is 1.
2. The composite bone repair material according to claim 1, characterized in that the inorganic component content is 65%.
3. The composite bone repair material according to claim 1, wherein the mass ratio of hydroxyapatite to whitlockite is 1:3, or 1:1, or 3:1.
4. the composite bone repair material of claim 1, wherein the whitlockite is prepared by reacting calcium hydroxide with magnesium hydroxide, adding phosphoric acid after the reaction, precipitating, centrifuging, washing, and freeze-drying to obtain whitlockite powder.
5. The composite bone repair material according to claim 1, wherein the hydroxyapatite is prepared by a chemical precipitation method using calcium nitrate and trisodium phosphate as raw materials.
6. A method of preparing the composite bone repair material according to any one of claims 1 to 5, wherein the method of preparation comprises a continuous reaction section and a foaming section:
a reaction section: adding the following reaction raw materials into a reactor in sequence: uniformly mixing hydroxyapatite, whitlockite and castor oil, and adding isophorone diisocyanate, a catalyst and a chain extender; the reaction section is carried out in an oil bath and stirring;
a foaming section: and adding a foaming agent into the reaction section, and then placing the reaction section into an oven for foaming to prepare the composite bone repair material.
7. The method for preparing the composite bone repair material according to claim 6, wherein the catalyst is stannous octoate, the chain extender is 1, 4-butanediol, and the foaming agent is water; the catalyst accounts for 0.1-0.3% of the mass of the reaction raw materials, the chain extender accounts for 2-3% of the mass of the reaction raw materials, and the water accounts for 0.5-1% of the mass of the reaction raw materials.
8. The method for preparing the composite bone repair material according to claim 6, wherein the temperature of the reaction section is 60-80 ℃ and the reaction time is 3-6h.
9. The method for preparing a composite bone repair material according to claim 6, wherein the foaming section temperature is 60-80 ℃ and the foaming time is 12-24h.
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