CN111298199A - Temporary implant for orthopedics department and preparation method thereof - Google Patents
Temporary implant for orthopedics department and preparation method thereof Download PDFInfo
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Abstract
The invention provides an orthopedic temporary implant and a preparation method thereof, belonging to the technical field of medical materials. The orthopedic temporary implant is an injectable composite temperature-sensitive hydrogel composed of chitosan quaternary ammonium salt, quaternary ammonium salt modified nano hydroxyapatite and an amphoteric surfactant. After the injectable composite temperature-sensitive hydrogel is injected into a human body, the quaternary ammonium salt on the surface of the chitosan quaternary ammonium salt and the phosphate radical on the surface of the quaternary ammonium salt modified nano hydroxyapatite form electrostatic interaction through anions and cations of the amphoteric surfactant, and the hydrogel with the porous three-dimensional cross-linked network structure is obtained. According to the invention, the temperature-sensitive hydrogel is formed by quaternary ammonium salt modification and mainly utilizing electrostatic action, so that the mechanical property of the hydrogel is improved, and meanwhile, the hydrogel is endowed with good antibacterial property; the amino acid type amphoteric surfactant is preferably used as an electrostatic crosslinking bridge, has good biocompatibility, can form a through crosslinking network, and further improves the mechanical property.
Description
Technical Field
The invention belongs to the technical field of biomedical materials, and relates to an orthopedic temporary implant and a preparation method thereof.
Background
The number of patients with bone defects caused by improper treatment of fracture and fracture after treatment, severe trauma, infection, bone tumor and the like is as many as ten million all the year around the world. Bone defect is a common disease, mainly is local bone loss caused by trauma and diseases (such as infection, tumor and the like), and is still one of the problems facing orthopedics due to high clinical morbidity and lack of an ideal treatment method. Although bone grafting (autologous bone grafting and allogeneic bone grafting) is a traditional treatment means for repairing bone defects and has good curative effect, the method still has obvious defects and limitations. Therefore, the search for ideal bone graft substitute materials is highly unpredictably needed.
Generally, hydrogels with temperature-sensitive properties can be injected into tissue or organ cavities in a minimally invasive surgical manner, and form solid fillers with specific shapes to match the cavities, which makes them satisfactory for various biomedical applications.Chitosan, a biodegradable natural polymer material with excellent properties, the hydrogels prepared therefrom have been widely used, particularly temperature-sensitive hydrogels prepared from chitosan/GP (β -sodium glycerophosphate), have been used as in situ gel scaffolds to repair or reconstruct cartilage, bone, nerve and skin defects, and as carriers for the delivery of drugs or bioactive molecules.
The Chinese patent with application number 201510252453.8 discloses an injectable porous-drug-loaded polymethyl methacrylate-based composite scaffold bone graft material and a preparation method thereof, wherein polymethyl methacrylate is used as a scaffold for providing mechanical support, and chitosan-based temperature-sensitive glue is used as a pore-forming agent and a carrier of a bone guiding material and a drug to form an injectable porous three-dimensional structure bone cement composite, which has good biocompatibility and mechanical properties, but poor biodegradability of polymethyl methacrylate.
Therefore, it is urgently needed to prepare a bone grafting material which has good biocompatibility, high mechanical property and matched degradation rate in vivo with a bone defect repair mechanism.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an orthopedic temporary implant and a preparation method thereof, wherein the temperature-sensitive hydrogel is formed by quaternary ammonium salt modification and mainly utilizing electrostatic action, so that the mechanical property of the hydrogel is improved, and meanwhile, the hydrogel is endowed with good antibacterial property; the amino acid type amphoteric surfactant is preferably used as an electrostatic crosslinking bridge, has good biocompatibility, can form a through crosslinking network, and further improves the mechanical property.
In order to achieve the purpose, the invention adopts the following technical scheme:
the orthopedics temporary implant is injectable composite temperature-sensitive hydrogel composed of chitosan quaternary ammonium salt, quaternary ammonium salt modified nano-hydroxyapatite and an amphoteric surfactant, after the injectable composite temperature-sensitive hydrogel is injected into a human body, the chitosan quaternary ammonium salt and the quaternary ammonium salt modified nano-hydroxyapatite form electrostatic action through the amphoteric surfactant, and hydrogel with a porous three-dimensional network structure is obtained.
As a further improvement of the invention, the mass ratio of the chitosan quaternary ammonium salt, the quaternary ammonium salt modified nano hydroxyapatite and the amphoteric surfactant is 100 (10-15) to (5-10).
As a further improvement of the invention, in the quaternary ammonium salt modified nano hydroxyapatite, the molar ratio of the quaternary ammonium salt to the nano hydroxyapatite is 1 (5-10).
As a further improvement of the present invention, the amphoteric surfactant is an amino acid type amphoteric surfactant.
As a further improvement of the invention, the quaternary ammonium salt is a silicone quaternary ammonium salt.
As a further improvement of the invention, the organosilicon quaternary ammonium salt is any one or more of organosilicon quaternary ammonium salt of trimethoxy silane containing C10-C18 alkyl and organosilicon quaternary ammonium salt of triethoxy silane containing C10-C18 alkyl.
A preparation method of the orthopedic temporary implant comprises the following steps:
s1, dissolving chitosan quaternary ammonium salt in deionized water to obtain a chitosan quaternary ammonium salt water solution;
s2, respectively preparing inorganic calciumAqueous salt solution and (NH)4)2HPO4Adjusting pH of the two solutions to 10-11 with ammonia water, and adding (NH) at molar ratio of calcium to phosphorus of 1.674)2HPO4Adding the water solution into an inorganic salt water solution of calcium, adding organosilicon quaternary ammonium salt, uniformly mixing, performing hydrothermal treatment for 4-16h at 90-180 ℃ in a high-pressure reaction kettle, and then performing centrifugal separation, washing and drying to obtain quaternary ammonium salt modified nano hydroxyapatite;
s3, adding the quaternary ammonium salt modified nano hydroxyapatite obtained in the step S2 and the amphoteric surfactant into the chitosan quaternary ammonium salt aqueous solution obtained in the step S1 according to the mass ratio of the chitosan quaternary ammonium salt, the quaternary ammonium salt modified nano hydroxyapatite and the amphoteric surfactant of 100 (10-15) to (5-10), and uniformly stirring to obtain the orthopedic temporary implant.
As a further improvement of the invention, in step S2, the molar ratio of the organosilicon quaternary ammonium salt to the calcium atoms is 1 (5-10).
As a further improvement of the present invention, in step S2, the modified inorganic salt is anhydrous calcium chloride.
As a further improvement of the invention, in step S1, the concentration of the chitosan quaternary ammonium salt aqueous solution is 20-45 mg/mL.
Advantageous effects
Compared with the prior art, the orthopedic temporary implant and the preparation method thereof provided by the invention have the following beneficial effects:
(1) the invention provides an orthopedic temporary implant, which is an injectable composite temperature-sensitive hydrogel composed of chitosan quaternary ammonium salt, quaternary ammonium salt modified nano hydroxyapatite and an amphoteric surfactant. After the injectable composite temperature-sensitive hydrogel is injected into a human body, the quaternary ammonium salt on the surface of the chitosan quaternary ammonium salt and the phosphate radical on the surface of the quaternary ammonium salt modified nano hydroxyapatite form electrostatic interaction through anions and cations of the amphoteric surfactant, and the hydrogel with the porous three-dimensional cross-linked network structure is obtained. According to the invention, the temperature-sensitive hydrogel is formed by quaternary ammonium salt modification and mainly utilizing electrostatic action, so that the mechanical property of the hydrogel is improved, and meanwhile, the hydrogel is endowed with good antibacterial property; the amino acid type amphoteric surfactant is preferably used as an electrostatic crosslinking bridge, has good biocompatibility, can form a through crosslinking network, and further improves the mechanical property.
(2) According to the invention, chitosan quaternary ammonium salt is used as a main body of the temperature-sensitive hydrogel, and the surface of the temperature-sensitive hydrogel is rich in amino, hydroxyl and quaternary ammonium salt cations; the specific surface area of the quaternary ammonium salt modified nano hydroxyapatite is large, the quaternary ammonium salt is not easy to agglomerate after being adsorbed on the surface, and the number of active points of electrostatic action is increased; the amphoteric surfactant contains cations and anions at the same time, can be used as a bridge for electrostatic action, and connects the chitosan quaternary ammonium salt and the quaternary ammonium salt modified nano hydroxyapatite to form a porous three-dimensional network structure, so that the mechanical strength of the hydrogel is remarkably improved.
(3) The invention adopts a hydrothermal method to prepare nano hydroxyapatite, and in the preparation process, organosilicon quaternary ammonium salt is added, and in the hydrothermal process, the organosilicon quaternary ammonium salt is a cationic surfactant, the molecule is in a long rod-shaped micelle structure in an aqueous solution, one end of the molecule is a positively charged hydrophilic head which has stronger affinity with water molecules, and the other end of the molecule is a hydrophobic tail which has weaker affinity with the water molecules. The organosilicon quaternary ammonium salt molecules are separated into cations and anions in an aqueous solution system, in the reaction process, the positively charged cations can be selectively adsorbed on the hydrophilic crystal face of the nano hydroxyapatite, and the formed hydroxyapatite precursor can continuously carry out chemical reaction, so that the hydroxyapatite is generated by being attached to the surface of the organosilicon quaternary ammonium salt micelle in a certain direction, and the prepared quaternary ammonium salt modified nano hydroxyapatite has large specific surface area, more active points and good antibacterial property.
Drawings
Fig. 1 is a graph showing the in vitro degradation rate of the orthopedic temporary implants prepared in example 1 and comparative examples 1 and 2.
Detailed Description
The technical solutions of the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments; all other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
The invention provides an orthopedic temporary implant, which is an injectable composite temperature-sensitive hydrogel composed of chitosan quaternary ammonium salt, quaternary ammonium salt modified nano-hydroxyapatite and an amphoteric surfactant.
After the injectable composite temperature-sensitive hydrogel is injected into a human body, under the stimulation of the temperature and the PH environment of the human body, the quaternary ammonium salt on the surface of the chitosan quaternary ammonium salt and the phosphate radical on the surface of the quaternary ammonium salt modified nano hydroxyapatite form electrostatic interaction through anions and cations of the amphoteric surfactant, and the hydrogel with the porous three-dimensional cross-linked network structure is obtained. According to the invention, the temperature-sensitive hydrogel is formed by quaternary ammonium salt modification and mainly utilizing electrostatic interaction, so that the mechanical property of the hydrogel is improved, and meanwhile, the hydrogel is endowed with good antibacterial property.
As a further improvement of the invention, the mass ratio of the chitosan quaternary ammonium salt, the quaternary ammonium salt modified nano hydroxyapatite and the amphoteric surfactant is 100 (10-15) to (5-10). The chitosan quaternary ammonium salt is used as a main body of the temperature-sensitive hydrogel, and the surface of the chitosan quaternary ammonium salt is rich in amino, hydroxyl and quaternary ammonium salt cations; the specific surface area of the quaternary ammonium salt modified nano hydroxyapatite is large, the quaternary ammonium salt is not easy to agglomerate after being adsorbed on the surface, and the number of active points of electrostatic action is increased; the amphoteric surfactant contains cations and anions at the same time, can be used as a bridge for electrostatic action, and connects the chitosan quaternary ammonium salt and the quaternary ammonium salt modified nano hydroxyapatite to form a porous three-dimensional network structure, so that the mechanical strength of the hydrogel is remarkably improved.
As a further improvement of the invention, in the quaternary ammonium salt modified nano hydroxyapatite, the molar ratio of the quaternary ammonium salt to the nano hydroxyapatite is 1 (5-10). The quaternary ammonium salt is added in the preparation process of the nano hydroxyapatite and is adsorbed on the surface of the nano hydroxyapatite along with the growth process of the nano hydroxyapatite, so that the surface activity and the antibacterial property are improved.
As a further improvement of the present invention, the amphoteric surfactant is an amino acid type amphoteric surfactant. The amino acid type amphoteric surfactant is preferably used as an electrostatic crosslinking bridge, has good biocompatibility, can form a through crosslinking network, and further improves the mechanical property.
As a further improvement of the invention, the quaternary ammonium salt is a silicone quaternary ammonium salt.
As a further improvement of the invention, the organosilicon quaternary ammonium salt is any one or more of organosilicon quaternary ammonium salt of trimethoxy silane containing C10-C18 alkyl and organosilicon quaternary ammonium salt of triethoxy silane containing C10-C18 alkyl. The organosilicon quaternary ammonium salt has good antibacterial property and biocompatibility.
A preparation method of the orthopedic temporary implant comprises the following steps:
s1, dissolving chitosan quaternary ammonium salt in deionized water to obtain a chitosan quaternary ammonium salt water solution with the concentration of 20-45 mg/mL;
s2, respectively preparing inorganic salt aqueous solution of calcium and (NH)4)2HPO4Adjusting pH of the two solutions to 10-11 with ammonia water, and adding (NH) at molar ratio of calcium to phosphorus of 1.674)2HPO4Adding the water solution into an inorganic salt water solution of calcium, adding organosilicon quaternary ammonium salt, uniformly mixing, performing hydrothermal treatment for 4-16h at 90-180 ℃ in a high-pressure reaction kettle, and then performing centrifugal separation, washing and drying to obtain quaternary ammonium salt modified nano hydroxyapatite;
in the hydrothermal process, the organosilicon quaternary ammonium salt is a cationic surfactant, the molecule is in a long rod-shaped micelle structure in an aqueous solution, one end of the molecule is a positively charged hydrophilic head which has strong affinity with water molecules, and the other end of the molecule is a hydrophobic tail which has weak affinity with the water molecules. The organosilicon quaternary ammonium salt molecules are separated into cations and anions in an aqueous solution system, in the reaction process, the positively charged cations can be selectively adsorbed on the hydrophilic crystal face of the nano hydroxyapatite, and the formed hydroxyapatite precursor can continuously carry out chemical reaction, so that the hydroxyapatite is attached to the surface of the organosilicon quaternary ammonium salt micelle to be generated according to a certain direction.
S3, adding the quaternary ammonium salt modified nano hydroxyapatite obtained in the step S2 and the amphoteric surfactant into the chitosan quaternary ammonium salt aqueous solution obtained in the step S1 according to the mass ratio of the chitosan quaternary ammonium salt, the quaternary ammonium salt modified nano hydroxyapatite and the amphoteric surfactant of 100 (10-15) to (5-10), and uniformly stirring to obtain the orthopedic temporary implant.
As a further improvement of the invention, in step S2, the molar ratio of the organosilicon quaternary ammonium salt to the calcium atoms is 1 (5-10).
As a further improvement of the present invention, in step S2, the modified inorganic salt is anhydrous calcium chloride.
The embodiment of the present invention will be described in detail below with reference to specific examples.
Example 1
An orthopedic temporary implant prepared by the steps of:
s1, dissolving chitosan quaternary ammonium salt in deionized water to obtain a chitosan quaternary ammonium salt water solution with the concentration of 30 mg/mL;
s2, respectively preparing an anhydrous calcium chloride aqueous solution with the concentration of 45mg/mL and (NH) with the concentration of 30mg/mL4)2HPO4Adjusting pH of the two aqueous solutions to 10 with ammonia water, and adding (NH) at molar ratio of calcium to phosphorus of 1.674)2HPO4Adding the aqueous solution into an anhydrous calcium chloride aqueous solution, adding hexadecyl trimethoxy silane quaternary ammonium salt according to the molar ratio of organosilicon quaternary ammonium salt to calcium atoms of 1:8, stirring and mixing uniformly, pouring the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal treatment at 120 ℃ for 12h, then carrying out centrifugal separation, washing with deionized water and absolute ethyl alcohol, and drying at 60 ℃ to obtain quaternary ammonium salt modified nano hydroxyapatite;
s3, adding the quaternary ammonium salt modified nano hydroxyapatite obtained in the step S2 and glutamic acid into the chitosan quaternary ammonium salt aqueous solution obtained in the step S1 according to the mass ratio of the chitosan quaternary ammonium salt, the quaternary ammonium salt modified nano hydroxyapatite and the amphoteric surfactant of 100:12:8, and uniformly stirring to obtain the orthopedic temporary implant.
Comparative example 1
An orthopedic temporary implant was prepared in a manner similar to that of example 1, except that in step S3, the amphoteric surfactant glutamic acid was not added, but the rest was substantially the same as in example 1 and thus will not be described herein.
Comparative example 2
An orthopedic temporary implant was fabricated by a method similar to that of example 1, except that, in step S2, the hexadecyl trimethoxy silane quaternary ammonium salt was not added, but the method was substantially the same as that of example 1 and thus will not be repeated herein.
The compressive strength and the modulus of elasticity of the orthopaedic temporary implant were respectively tested according to the standard GB/T1041-1992 at room temperature and 47% humidity using an Instron model 5697 universal tester. The test results are shown in table 1, and it can be seen that the compressive strength and the elastic modulus of the orthopaedic temporary implant prepared in example 1 are respectively as high as 18.98 ± 0.43MPa and 17.67 ± 0.36MPa, while the compressive strength and the elastic modulus of comparative example 1 and comparative example 2 are both significantly reduced, which indicates that the quaternary ammonium salt modification of nano-hydroxyapatite and the addition of the amphoteric surfactant to the hydrogel have significant effect on the mechanical strength of the hydrogel, and further proves that the electrostatic interaction can be improved by introducing a substance with cations or anions into each hydrogel component, thereby improving the crosslinking degree of the hydrogel and further improving the mechanical strength.
Table 1 results of mechanical strength test of example 1 and comparative examples 1 and 2
| Test specimen | Compressive strength (MPa) | Modulus of elasticity (MPa) |
| Example 1 | 18.98±0.43 | 17.67±0.36 |
| Comparative example 1 | 12.23±0.65 | 13.63±0.55 |
| Comparative example 2 | 13.68±0.52 | 14.87±0.64 |
And soaking the prepared orthopedic temporary implant in simulated body fluid, taking out samples every 24 hours, drying, weighing the weight of the orthopedic temporary implant, and calculating the accumulated degradation rate of the orthopedic temporary implant.
The in vitro degradation rates of example 1 and comparative examples 1 and 2 are shown in fig. 1, and it can be seen that the degradation rate of the orthopaedic temporary implant prepared in example 1 in simulated body fluid is significantly lower than that of comparative examples 1 and 2, because the quaternary ammonium salt modification of nano-hydroxyapatite and the addition of amphoteric surfactant to hydrogel can increase the degree of cross-linking of hydrogel, thereby reducing the degradation rate, and thus prolonging the bone defect repair time and repair effect.
Examples 2 to 3
Examples 2-3 provide orthopedic temporary implants, which are prepared according to a method different from that of example 1 in that, in step S2, the molar ratio of the silicone quaternary ammonium salt to the calcium atom is shown in table 2, and the rest is substantially the same as example 1, and thus, the description thereof is omitted.
Table 2 results of mechanical strength test of examples 2 to 3
As can be seen from table 2, as the molar ratio of the organosilicon quaternary ammonium salt to the calcium atoms increases and as the content of the organosilicon quaternary ammonium salt increases, the mechanical strength of the orthopaedic temporary implant tends to increase gradually, because during the growth process of hydroxyapatite, the organosilicon quaternary ammonium salt can be selectively adsorbed on the hydrophilic crystal face of the nano hydroxyapatite, reducing the agglomeration property thereof, increasing the surface active sites, and thus increasing the degree of crosslinking. However, the content of the organosilicon quaternary ammonium salt is too much, which is not beneficial to the growth of the nano hydroxyapatite.
Examples 4 to 5
Examples 4 to 5 provide orthopedic temporary implants, which are different from example 1 in that, in step S3, the mass ratio of the chitosan quaternary ammonium salt, the quaternary ammonium salt modified nano hydroxyapatite and the amphoteric surfactant is shown in table 3, and the rest is substantially the same as example 1, and thus, the description thereof is omitted.
Table 3 results of mechanical strength test of examples 4 to 5
As can be seen from table 3, the mechanical strength of the orthopaedic temporary implant shows a tendency to increase gradually with the increase of the content of the amphoteric surfactant, because the amphoteric surfactant, which serves as a bridge of the hydrogel cross-linked body, can cross-link the chitosan quaternary ammonium salt and the quaternary ammonium salt-modified hydroxyapatite into a three-dimensional network structure by electrostatic interaction, thereby improving the mechanical strength.
In conclusion, the invention takes the chitosan quaternary ammonium salt as the main body of the temperature-sensitive hydrogel, and the surface of the chitosan quaternary ammonium salt is rich in amino, hydroxyl and quaternary ammonium salt cations; the specific surface area of the quaternary ammonium salt modified nano hydroxyapatite is large, the quaternary ammonium salt is not easy to agglomerate after being adsorbed on the surface, and the number of active points of electrostatic action is increased; the amphoteric surfactant contains cations and anions at the same time, can be used as a bridge for electrostatic action, and connects the chitosan quaternary ammonium salt and the quaternary ammonium salt modified nano hydroxyapatite to form a porous three-dimensional network structure, so that the mechanical strength of the hydrogel is remarkably improved. The temperature-sensitive hydrogel is modified by quaternary ammonium salt, mainly utilizes the electrostatic effect to form the temperature-sensitive hydrogel, and endows the hydrogel with good antibacterial property while improving the mechanical property of the hydrogel; the amino acid type amphoteric surfactant is preferably used as an electrostatic crosslinking bridge, has good biocompatibility, can form a through crosslinking network, and further improves the mechanical property.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The orthopedic temporary implant is characterized by being injectable composite temperature-sensitive hydrogel consisting of chitosan quaternary ammonium salt, quaternary ammonium salt modified nano-hydroxyapatite and an amphoteric surfactant, wherein after the injectable composite temperature-sensitive hydrogel is injected into a human body, the chitosan quaternary ammonium salt and the quaternary ammonium salt modified nano-hydroxyapatite form electrostatic action through the amphoteric surfactant to obtain hydrogel with a porous three-dimensional network structure.
2. The orthopedic temporary implant of claim 1, wherein the mass ratio of said quaternary ammonium salt of chitosan, said quaternary ammonium salt modified nano-hydroxyapatite and said amphoteric surfactant is 100 (10-15) to (5-10).
3. The orthopedic temporary implant of claim 1, wherein the molar ratio of quaternary ammonium salt to nano-hydroxyapatite in said quaternary ammonium salt modified nano-hydroxyapatite is 1 (5-10).
4. An orthopaedic temporary implant according to claim 1, wherein said amphoteric surfactant is an amino acid type amphoteric surfactant.
5. An orthopaedic temporary implant according to claim 1, wherein said quaternary ammonium salt is a silicone quaternary ammonium salt.
6. An orthopaedic temporary implant according to claim 5, wherein said quaternary silicone salt is any one or more of a quaternary silicone salt of trimethoxysilane containing C10-C18 alkyl groups and a quaternary silicone salt of triethoxysilane containing C10-C18 alkyl groups.
7. A method for preparing an orthopaedic temporary implant according to any one of claims 1 to 6, comprising the steps of:
s1, dissolving chitosan quaternary ammonium salt in deionized water to obtain a chitosan quaternary ammonium salt water solution;
s2, respectively preparing inorganic salt aqueous solution of calcium and (NH)4)2HPO4Adjusting pH of the two solutions to 10-11 with ammonia water, and adding (NH) at molar ratio of calcium to phosphorus of 1.674)2HPO4Adding the water solution into an inorganic salt water solution of calcium, adding organosilicon quaternary ammonium salt, uniformly mixing, performing hydrothermal treatment for 4-16h at 90-180 ℃ in a high-pressure reaction kettle, and then performing centrifugal separation, washing and drying to obtain quaternary ammonium salt modified nano hydroxyapatite;
s3, adding the quaternary ammonium salt modified nano hydroxyapatite obtained in the step S2 and the amphoteric surfactant into the chitosan quaternary ammonium salt aqueous solution obtained in the step S1 according to the mass ratio of the chitosan quaternary ammonium salt, the quaternary ammonium salt modified nano hydroxyapatite and the amphoteric surfactant of 100 (10-15) to (5-10), and uniformly stirring to obtain the orthopedic temporary implant.
8. The method for producing an orthopedic temporary implant according to claim 7, wherein in step S2, the molar ratio of said quaternary ammonium silicone salt to calcium atoms is 1 (5-10).
9. The method for preparing an orthopedic temporary implant according to claim 7, wherein in step S2, the modified inorganic salt is anhydrous calcium chloride.
10. The method for preparing an orthopedic temporary implant according to claim 7, wherein in step S1, the concentration of said aqueous solution of chitosan quaternary ammonium salt is 20-45 mg/mL.
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