CN113198052A - Ferroferric oxide/polytetrahydrofuran composite bone repair material and application thereof - Google Patents
Ferroferric oxide/polytetrahydrofuran composite bone repair material and application thereof Download PDFInfo
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Abstract
The invention relates to a ferroferric oxide/polytetrahydrofuran composite bone repair material and application thereof, belonging to the field of medical materials for bone injury. The invention provides a ferroferric oxide/polytetrahydrofuran composite bone repair material. The composite system utilizes the magnetic ferroferric oxide and polytetrahydrofuran to be compounded, the mechanical property of the composite material can be enhanced under the action of an external magnetic field, osteoblast proliferation is promoted, the bone repair process is accelerated, simultaneously, the composite system has excellent biological compatibility, no cytotoxicity and good bone conductivity and bone inductivity, the composite material three-dimensional porous structure can also be prepared by compounding the nano particles and the polytetrahydrofuran through polyurethane crosslinking reaction, the obtained porous composite material has uniform pore distribution, the pore size is matched with the pore size on the surface of a bone, the composite system has good biocompatibility and degradability, the preparation process is simple, the composite system is easy to process and form, the composite material has good mechanical property, can meet the requirement of bone loading, and can be used for processing bone plates, bone screws, intraosseous bars, brackets and the like required by bone defect bearing and fixation, is suitable for the field of medical materials for bone tissue injury, and provides a feasible and effective novel ferroferric oxide/polytetrahydrofuran composite bone repair material for the field of bone repair materials.
Description
Technical Field
The invention relates to a ferroferric oxide/polytetrahydrofuran composite bone repair material and application thereof, belonging to the field of medical materials for bone injury.
Background
At present, the conditions of bone tissue damage and the like caused by trauma, infection, osteoporosis and the like are remarkably increased, medical materials are more and more widely regarded, wherein the repair and replacement of bone defects by using artificial bone substitute materials become the key research point in the medical orthopedics field and are also effective means for treating orthopedics diseases such as severe trauma, congenital defects, bone tumors, osteomyelitis and the like. The ideal bone repair material has good biocompatibility, good bone induction and bone conduction performances, and can promote the growth of new bone tissues and induce the formation of osteoblasts. In addition, the ideal bone repair material needs to have good moldability to be processed into various sizes and shapes required clinically.
Polyurethane (PU) materials are typically polymerized from hard-segment materials containing diisocyanates and soft-segment materials containing hydroxyl groups. The degradable block polyurethane has strong structural adjustability and flexible design scheme, can adjust the hardness or elasticity of the material and adjust the degradation rate by adjusting the composition proportion or variety of the soft and hard sections, can provide a collagen-like environment for the adhesion of osteoblasts or bone marrow stromal stem cells due to the characteristics and good biocompatibility of micro-areas, and has good application prospect in the field of bone repair. The polytetrahydrofuran-based polyurethane is emphasized in the field of biomedicine due to good biocompatibility and processability and no cytotoxicity, and a bone repair material compounded by polytetrahydrofuran and inorganic calcium salt is often used for treating bone injury in clinical application at present. The action mechanism on the one hand, polytetrahydrofuran has good biocompatibility, good organic polymer compatibility and biodegradability, can be used as a cell growth supporting material, and can change the mechanical and degradation properties thereof by adjusting the hard segment content of polytetrahydrofuran-based polyurethane soft segment to meet different clinical requirements, and Mi, HY et al, in Biocompatible, degradable thermoplastic polyurethane based on polyurethane-block-polyurethane-copolymer for soft tissue engineering (Mi Hao-Yang, jin, Napiwomark Brett N, hagy Breana S, Chen Guojun, Turn Liang-Shell, Biocompatible, degradable thermoplastic polyurethane based on polyurethane-polymer J. composite of polytetrahydrofuran, Polytetrahydrofuran J. polyethylene-copolymer, J. polyethylene-polyester, polyethylene-polyester copolymer, polyethylene-polyester-, the research shows that the thermal degradation performance and the water degradation performance of the material are greatly improved, but the mechanical strength of the material is not ideal. At present, the composite material has obtained a good research result, but certain defects still exist, such as poor plasticity, weak mechanical strength, complex processing and preparation technology and the like, and a new direction needs to be researched from a new material, so that a new idea and a new method are provided for further realizing clinical treatment application.
Ferroferric oxide nano particles are a novel biomedical material, can stably exist in a human body, have good biocompatibility and poison effects on organisms, have a promoting effect on bone repair under the action of an external magnetic field as magnetic nano particles, and are prepared by Wutao by a hydrothermal method (preparation of a nano carbon-based magnetic composite material and application in calcium phosphate bone cement [ D ]. transport university in southwest, 2017 ]). Chinese patent CN201710604641.1 utilizes ferroferric oxide to prepare a bone repair material, and the material has good magnetic properties and biocompatibility, can induce the formation of bone tissues, but still has certain defects, such as poor mechanical properties, limited forming capacity and the like.
The ferroferric oxide/polytetrahydrofuran composite bone repair material is prepared by compounding ferroferric oxide with good biocompatibility and polytetrahydrofuran. The ferroferric oxide and the polytetrahydrofuran have good interface compatibility, the high molecular polymer is taken as the matrix of the composite material and is assisted by the functional filler, so that the ferroferric oxide and the polytetrahydrofuran are combined more closely, the mechanical strength of the composite material is improved to meet the requirement of bone load, the biological performance of the composite material can be improved, the problem of slow degradation of the high molecular polymer is solved, the mechanical and degradation performances of the polytetrahydrofuran-based polyurethane can be changed to meet different clinical requirements by changing the content of the hard segment of the soft segment of the polytetrahydrofuran-based polyurethane, and the composite bone repair material is prepared by a gas spontaneous foaming forming technology so that the forming process is simple, the conditions are mild, and the composite bone repair material is nontoxic and harmless.
The ferroferric oxide/polytetrahydrofuran-based polyurethane composite bone repair material provided by the invention has the advantages that the pore diameter of the large pores is 200-600 mu m, the pore diameter of the small pores is 15-150 mu m, the pore size of the small pores is matched with the pore size of the surface of bone cells, the processing is easy, the growth of new bone tissues is promoted, and the generation of osteoblasts is induced. In addition, the mechanical and degradation properties of the polytetrahydrofuran-based polyurethane can be changed by changing the content of the hard segment of the soft segment so as to meet different clinical requirements, the composite material has strong plasticity and can be repeatedly molded, and bone repair materials with different shapes and sizes are prepared so as to meet the clinical requirements, and the composite material can be used for processing bone plates, bone screws, intraosseous rods, brackets and the like required by bone defect bearing and fixing. The ferroferric oxide/polytetrahydrofuran-based polyurethane composite bone repair material prepared by the invention provides a feasible and effective new material for the field of bone injury medical materials, and is beneficial to expanding the application and development of the field of bone repair materials.
Disclosure of Invention
The invention provides a ferroferric oxide/polytetrahydrofuran composite bone repair material and a preparation method thereof, aiming at the defects of the existing bone repair composite material. The composite material consists of polytetrahydrofuran and ferroferric oxide, wherein the ferroferric oxide is spherical nano particles, and the molecular weight of the polytetrahydrofuran is 3000-4000. The ferroferric oxide content is 2.5-10% by mass percent, and the balance is polytetrahydrofuran content. The ferroferric oxide/polytetrahydrofuran composite bone repair material provided by the invention has the porosity of 68-85% and the pore size of 10-600 microns.
The invention relates to a preparation method of a ferroferric oxide/polytetrahydrofuran composite bone repair material, which comprises the following specific steps:
(1) weighing polytetrahydrofuran and ferroferric oxide in a corresponding compound proportion;
(2) measuring an organic solvent by using a measuring cylinder, pouring the organic solvent into a beaker, pouring the weighed polytetrahydrofuran into the flask, and stirring until the polytetrahydrofuran is completely dissolved to obtain a transparent polytetrahydrofuran solution; the stirring speed is 60-300 r/min;
(3) pouring the weighed ferroferric oxide with the corresponding proportion into the polytetrahydrofuran solution in the step (2);
(4) adding a certain amount of hexamethylene diisocyanate and a catalyst into a polytetrahydrofuran solution, heating and stirring for 30-60 min at 80-90 ℃ under the protection of nitrogen, then adding a chain extender which is 2-4% of the mass of a soft-segment material, continuously reacting, and evaporating a solvent to obtain a brown viscous mixture, wherein the chain extender is 1, 4-butanediol; the catalyst is stannous octoate;
(5) adding a certain amount of water serving as a foaming agent into the brown viscous mixture obtained in the step (4), and simultaneously injecting the mixture into a mold to be foamed and molded in an oven at the temperature of 110-120 ℃;
(6) curing the reaction mixture obtained in the step (5) at the temperature of 110-120 ℃ for 12-24 hours to obtain the ferroferric oxide/polytetrahydrofuran composite bone repair material.
The invention has the beneficial effects that:
the invention provides a ferroferric oxide/polytetrahydrofuran composite bone repair material. The composite system is compounded by magnetic ferroferric oxide and polytetrahydrofuran, so that the mechanical property of the composite material can be enhanced, osteoblast proliferation is promoted under the action of an external magnetic field, and the bone repair process is accelerated; in addition, the polytetrahydrofuran is a high molecular material with good biological compatibility and no cytotoxicity, is crosslinked and foamed by using aliphatic isocyanate, avoids potential cytotoxicity caused by aromatic isocyanate, can also adjust the content of foaming agent water, and prepares a bone repair material with uniform pore size and distribution and matched with the pore size on the surface of a bone; in addition, the mechanical property and degradation rate of the composite material can be improved by means of adjusting the ratio of soft segments to soft segments of the composite material and the like, so that different clinical requirements can be met.
Therefore, the ferroferric oxide/polytetrahydrofuran composite bone repair material prepared by the invention can promote osteoblast proliferation to accelerate the bone repair process, has good biocompatibility, is simple in process for preparing a three-dimensional porous composite material by using a foaming method, is easy to machine and form, has good mechanical property, can meet the requirements of bone load, has strong material plasticity, can be used for preparing bone plates, bone screws, bone internal rods, brackets and the like required by bone defect bearing and fixing by changing the mechanical property of the composite material by adjusting the ratio of soft segments and soft segments of the composite material to meet different clinical requirements, is suitable for the field of bone injury repair medical materials, and provides a feasible and effective novel bone repair material for the field of bone repair materials.
Description of the drawings:
FIG. 1 is an XRD (X-ray diffraction) pattern of a ferroferric oxide/polytetrahydrofuran composite bone repair material in example 1 of the invention;
FIG. 2 is an SEM photograph of a ferroferric oxide/polytetrahydrofuran composite bone repair material in example 1 of the invention;
FIG. 3 is an FTIR chart of the ferroferric oxide/polytetrahydrofuran composite bone repair material of example 1 of the present invention;
FIG. 4 is a stress-strain curve diagram of the ferroferric oxide/polytetrahydrofuran composite bone repair material in embodiments 1-4 of the present invention.
Fig. 5 is a TGA diagram of the ferroferric oxide/polytetrahydrofuran composite bone repair material according to example 1 of the present invention.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the contents.
Example 1:
the ferroferric oxide/polytetrahydrofuran composite bone repair material in the embodiment is composed of polytetrahydrofuran and ferroferric oxide, wherein the content of the ferroferric oxide is 10% by mass, and the balance is the polytetrahydrofuran; wherein the ferroferric oxide is spherical nano particles, and the molecular weight of the polytetrahydrofuran is 4000. The method comprises the following specific steps:
(1) 40g of polytetrahydrofuran and 4.44g of ferroferric oxide;
(2) measuring an organic solvent by using a measuring cylinder, pouring the organic solvent into a beaker, pouring the weighed polytetrahydrofuran into the flask, and stirring until the polytetrahydrofuran is completely dissolved to obtain a transparent polytetrahydrofuran solution; the stirring speed is 300 r/min;
(3) pouring weighed ferroferric oxide into the polytetrahydrofuran solution in the step (2);
(4) adding 3.36g of hexamethylene diisocyanate and 7 drops of stannous octoate into a polytetrahydrofuran solution, heating and stirring at 90 ℃ for 60min under the protection of nitrogen, and evaporating a solvent to obtain a brown viscous mixture;
(5) adding water with the mass fraction of 2% of the system as a foaming agent into the brown viscous mixture in the step (4), and simultaneously injecting the mixture into a mold to be foamed and molded in an oven at 120 ℃;
(6) and (5) curing the reaction mixture at 120 ℃ for 24 hours to obtain the ferroferric oxide/polytetrahydrofuran composite bone repair material.
Porosity determination using an electron density balance the porosity of the ferriferrous oxide/polytetrahydrofuran composite bone repair material prepared in this example was 76.36%.
The compressive strength of the ferroferric oxide/polytetrahydrofuran composite bone repair material prepared in the example is 156.2996MPa by utilizing the test of an electronic universal tester to measure the compressive strength.
Fig. 1 is an XRD spectrum of a ferroferric oxide/polytetrahydrofuran composite bone repair material prepared in this example.
FIG. 2 is an SEM picture of a ferroferric oxide/polytetrahydrofuran composite bone repair material prepared in the example, and it can be seen from the SEM picture that the material has a communicated pore structure, the pore size is in a micron level, and the range of the pore size is approximately 15-100 μm.
FIG. 3 is an infrared spectrum of a ferroferric oxide/polytetrahydrofuran composite bone repair material prepared in the example.
The ferroferric oxide/polytetrahydrofuran composite bone repair material prepared in the example is made into a cylindrical sample with the length-diameter ratio of about 1:1 by a knife and a sand paper, and the cylindrical sample is pressed by a universal testing machine under the conditions of the control speed of 1kn/s and the displacement speed of 1mm/min to prepare the compressive strength of the corresponding sample. The different compounding ratios were measured using 6 parallel samples, and the average value was taken as the compressive strength of the composite. The ferroferric oxide/polytetrahydrofuran-based polyurethane composite material shows better mechanical property, and meanwhile, the mechanical property of the composite material is greatly related to the pore structure of the composite material, and the higher the porosity is, the poorer the mechanical property is, so that the porosity is consistent with the porosity in each example of the invention (figure 4).
Fig. 5 is a thermogravimetric analysis spectrum of a ferroferric oxide/polytetrahydrofuran composite bone repair material prepared in the example.
Example 2:
the ferroferric oxide/polytetrahydrofuran composite bone repair material in the embodiment is composed of polytetrahydrofuran and ferroferric oxide, wherein the content of the ferroferric oxide is 2.5% by mass, and the balance is the polytetrahydrofuran; wherein the ferroferric oxide is spherical nano particles, and the molecular weight of the polytetrahydrofuran is 4000. The method comprises the following specific steps:
(1) 40g of polytetrahydrofuran and 1.03g of ferroferric oxide;
(2) measuring an organic solvent by using a measuring cylinder, pouring the organic solvent into a beaker, pouring the weighed polytetrahydrofuran into the flask, and stirring until the polytetrahydrofuran is completely dissolved to obtain a transparent polytetrahydrofuran solution; the stirring speed is 200 r/min;
(3) pouring weighed ferroferric oxide into the polytetrahydrofuran solution in the step (2);
(4) adding 3.36g of hexamethylene diisocyanate and 7 drops of stannous octoate into a polytetrahydrofuran solution, heating and stirring at 80 ℃ for 30min under the protection of nitrogen, and evaporating a solvent to obtain a brown viscous mixture;
(5) adding water with the mass fraction of 1% of the system as a foaming agent into the brown viscous mixture in the step (4), and simultaneously injecting the mixture into a mold to be foamed and molded in a drying oven at 110 ℃;
(6) and (5) curing the reaction mixture at 120 ℃ for 12 hours to obtain the ferroferric oxide/polytetrahydrofuran composite bone repair material.
Porosity determination using an electron density balance the porosity of the ferriferrous oxide/polytetrahydrofuran composite bone repair material prepared in this example was 68.55%.
The compressive strength of the ferroferric oxide/polytetrahydrofuran composite bone repair material prepared in the example is 81.5022MPa by utilizing the test of an electronic universal tester to measure the compressive strength.
Example 3:
the ferroferric oxide/polytetrahydrofuran composite bone repair material in the embodiment is composed of polytetrahydrofuran and ferroferric oxide, wherein the ferroferric oxide content is 5% by mass, and the balance is polytetrahydrofuran; wherein the ferroferric oxide is spherical nano particles, and the molecular weight of the polytetrahydrofuran is 4000. The method comprises the following specific steps:
(1) 40g of polytetrahydrofuran and 2.11g of ferroferric oxide;
(2) measuring an organic solvent by using a measuring cylinder, pouring the organic solvent into a beaker, pouring the weighed polytetrahydrofuran into the flask, and stirring until the polytetrahydrofuran is completely dissolved to obtain a transparent polytetrahydrofuran solution; the stirring speed is 250 r/min;
(3) pouring weighed ferroferric oxide into the polytetrahydrofuran solution in the step (2);
(4) adding 3.36g of hexamethylene diisocyanate and 7 drops of stannous octoate into a polytetrahydrofuran solution, heating and stirring at 90 ℃ for 40min under the protection of nitrogen, and evaporating a solvent to obtain a brown viscous mixture;
(5) adding water with the mass fraction of 1% of the system as a foaming agent into the brown viscous mixture in the step (4), and simultaneously injecting the mixture into a mold to be foamed and molded in an oven at 120 ℃;
(6) and (5) curing the reaction mixture at 120 ℃ for 18 hours to obtain the ferroferric oxide/polytetrahydrofuran composite bone repair material.
Porosity determination using an electron density balance the porosity of the ferriferrous oxide/polytetrahydrofuran composite bone repair material prepared in this example was 84.89%.
The compressive strength of the ferroferric oxide/polytetrahydrofuran composite bone repair material prepared in the example is 107.4445MPa by utilizing the test of an electronic universal tester to measure the compressive strength.
Example 4:
the ferroferric oxide/polytetrahydrofuran composite bone repair material in the embodiment is composed of polytetrahydrofuran and ferroferric oxide, wherein the ferroferric oxide content is 0% and the balance is polytetrahydrofuran in percentage by mass; wherein the ferroferric oxide is spherical nano particles, and the molecular weight of the polytetrahydrofuran is 4000. The method comprises the following specific steps:
(1) 40g of polytetrahydrofuran and 0g of ferroferric oxide;
(2) measuring an organic solvent by using a measuring cylinder, pouring the organic solvent into a beaker, pouring the weighed polytetrahydrofuran into the flask, and stirring until the polytetrahydrofuran is completely dissolved to obtain a transparent polytetrahydrofuran solution; the stirring speed is 300 r/min;
(3) pouring weighed ferroferric oxide into the polytetrahydrofuran solution in the step (2);
(4) adding 3.36g of hexamethylene diisocyanate and 7 drops of stannous octoate into a polytetrahydrofuran solution, heating and stirring at 90 ℃ for 60min under the protection of nitrogen, and evaporating a solvent to obtain a brown viscous mixture;
(5) adding water with the mass fraction of 2% of the system as a foaming agent into the brown viscous mixture in the step (4), and simultaneously injecting the mixture into a mold to be foamed and molded in an oven at 120 ℃;
(6) and (5) curing the reaction mixture at 120 ℃ for 24 hours to obtain the ferroferric oxide/polytetrahydrofuran composite bone repair material.
Porosity determination using an electron density balance the porosity of the ferriferrous oxide/polytetrahydrofuran composite bone repair material prepared in this example was 72.58%.
The compressive strength of the ferroferric oxide/polytetrahydrofuran composite bone repair material prepared in the example is 100.4829MPa by utilizing the test of an electronic universal tester to measure the compressive strength.
The embodiment is a composite bone repair material prepared from pure polytetrahydrofuran, is a control test group, and can be used as data reference of other test groups.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A ferroferric oxide/polytetrahydrofuran composite bone repair material is characterized in that: the material consists of polytetrahydrofuran and ferroferric oxide nanoparticles, wherein the content of the ferroferric oxide nanoparticles is 2.5-10% by mass, and the balance is the polytetrahydrofuran content.
2. The ferroferric oxide/polytetrahydrofuran-based polyurethane composite repair material according to claim 1, characterized in that: the ferroferric oxide component is spherical nanocrystal with the particle size of 5-10 nm.
3. The ferroferric oxide/polytetrahydrofuran composite bone repair material according to claim 1, characterized in that: the polyurethane is formed by co-polymerizing a hard block material of aliphatic diisocyanate and a polymer soft block material contained in hydroxyl-containing glycols, wherein the molar ratio of isocyanate groups in the hard block material to hydroxyl groups in the degradable soft block material is (2-6): 1, preferably (4-5): 1, and the molar ratio is as follows: the hard segment material comprises hexamethylene diisocyanate, and the soft segment material is polytetrahydrofuran with the molecular weight of 3000-4000.
4. The ferroferric oxide/polytetrahydrofuran composite bone repair material according to claim 1, characterized in that: the compressive strength is 81-156 MPa.
5. The ferroferric oxide/polytetrahydrofuran composite bone repair material according to claim 1, characterized in that: the pore size is 10 to 600 μm.
6. The ferroferric oxide/polytetrahydrofuran composite bone repair material according to claim 1, characterized in that: the porosity is 68-85%.
7. A preparation method of the ferroferric oxide/polytetrahydrofuran-based polyurethane bone-knitting repair material according to claims 1-6, characterized by comprising the following steps:
(1) respectively weighing polytetrahydrofuran and ferroferric oxide with corresponding compound proportion;
(2) measuring an organic solvent by using a measuring cylinder, pouring the organic solvent into a beaker, pouring the weighed polytetrahydrofuran into the flask, and stirring until the polytetrahydrofuran is completely dissolved to obtain a transparent polytetrahydrofuran solution; the stirring speed is 60-300 r/min;
(3) pouring the weighed ferroferric oxide with the corresponding proportion into the polytetrahydrofuran solution in the step (2);
(4) adding a certain amount of hexamethylene diisocyanate and a catalyst into a polytetrahydrofuran solution, heating and stirring at 80-90 ℃ for 30-60 min under the protection of nitrogen, then adding a chain extender which is 2-4% of the mass of a soft segment material, continuously reacting, and evaporating a solvent to obtain a brown viscous mixture;
(5) adding a certain amount of foaming agent into the brown viscous mixture obtained in the step (4), and simultaneously injecting the mixture into a mold to be foamed and molded in an oven at the temperature of 110-120 ℃;
(6) curing the reaction mixture obtained in the step (5) at the temperature of 110-120 ℃ for 12-24 hours to obtain the ferroferric oxide/polytetrahydrofuran composite bone repair material.
8. The preparation method of the ferroferric oxide/polytetrahydrofuran composite bone repair material according to claim 6, characterized by comprising the following steps: the ferroferric oxide component is spherical nanocrystal with the particle size of 5-10 nm.
9. The preparation method of the ferroferric oxide/polytetrahydrofuran composite bone repair material according to claim 6, characterized by comprising the following steps: in the step (4), the chain extender is 1, 4-butanediol; the catalyst is stannous octoate; the reaction heating temperature is set to be 80-90 ℃; in the step (5), the foaming agent is water; in the step (6), the foaming agent reaction comprises a reaction at 110-120 ℃ for 12-24 hours.
10. The ferroferric oxide/polytetrahydrofuran composite bone repair material according to claims 1-6, which can be applied to the field of bone injury medical materials of minimally invasive surgery and processed into bone plates, bone screws, intraosseous rods, brackets and the like required for bearing and fixing bone defects.
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