CN117624634B - Polysulfone hydroxyapatite polymer and preparation method and application thereof - Google Patents
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- 229920002492 poly(sulfone) Polymers 0.000 title claims abstract description 99
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Abstract
The invention discloses a polysulfone hydroxyapatite polymer and a preparation method and application thereof, and belongs to the technical field of polysulfone hydroxyapatite polymers. The preparation of the polysulfone hydroxyapatite polymer comprises the following steps: reacting the preparation raw materials of the polysulfone hydroxyapatite polymer at 1250-1350 ℃; every 100 parts of preparation raw materials comprise 10-20 parts of polysulfone and 0.5-10 parts of hydroxyapatite, and the balance of N-methylpyrrolidone. The method is simple and easy to operate, and the prepared polysulphone hydroxyapatite polymer has moderate number of pores and higher tensile property, and can be used for replacing hydroxyapatite to prepare related materials or instruments for treating diseases such as bone injury, bone defect and the like.
Description
Technical Field
The invention relates to the technical field of polysulfone hydroxyapatite polymers, in particular to a polysulfone hydroxyapatite polymer and a preparation method and application thereof.
Background
Bone defects refer to estimates of truly greater than 2mm in length or greater than 50% in bone circumference, often due to severe open fractures, osteomyelitis, bone tumor removal, and congenital diseases. At present, bone defects are mainly treated by adopting a repairing and reconstructing method, but the problems of complex operation, long treatment period, postoperative complications, poor postoperative soft tissues and the like are still clinical treatment problems, the technical development of biological materials and biological treatment in recent years, and especially the bone tissue engineering technology and stem cell technology provide a brand-new treatment idea for treating bone defects.
The main components of human bone are calcium phosphate mineral and organic matrix containing type I collagen fiber, and hydroxyapatite is the main inorganic component of bone, which has been proved to have good cell affinity, no rejection reaction occurs in the carrier, and the bone has been promoted to adhere and proliferate, and is directly combined with bone, so that it has been widely used as a substitute material for bone grafting.
However, the clinical use of hydroxyapatite is limited because it is fragile, not fatigue resistant and the new bone formed in the porous hydroxyapatite network cannot withstand the mechanical load required for remodeling.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a polysulfone hydroxyapatite polymer and a preparation method and application thereof, which are used for solving or improving the technical problems.
The application can be realized as follows:
in a first aspect, the present application provides a method for preparing a polysulfone hydroxyapatite polymer, comprising the steps of:
reacting the preparation raw materials of the polysulfone hydroxyapatite polymer at 1250-1350 ℃;
every 100 parts of preparation raw materials comprise 10-20 parts of polysulfone and 0.5-10 parts of hydroxyapatite, and the balance of N-methylpyrrolidone.
In alternative embodiments, the mass ratio of polysulfone to hydroxyapatite is 9:1 or 3:1.
In an alternative embodiment, the mass ratio of polysulfone to hydroxyapatite is 3:1.
In an alternative embodiment, the hydroxyapatite is P81B grade HA; and/or polysulfone is Ultrason S2010.
In an alternative embodiment, the temperature is raised to 1250-1350 ℃ at a rate of 55-65 ℃/h.
In an alternative embodiment, the reaction time is from 6 to 10 hours.
In an alternative embodiment, after the reaction, the temperature is reduced to room temperature at a rate of 115-125 ℃ per hour.
In a second aspect, the present application provides a polysulfone hydroxyapatite polymer prepared by the method of any of the preceding embodiments.
In a third aspect, the present application provides the use of a polysulfone hydroxyapatite polymer as in the previous embodiments for the preparation of an orthopaedic device or orthopaedic material.
In a fourth aspect, the present application provides a bone tissue engineering scaffold, the preparation raw material of which comprises the polysulfone hydroxyapatite polymer of the previous embodiment.
The beneficial effects of this application include:
the preparation method of the polysulphone hydroxyapatite polymer is simple and easy to operate, and the prepared polysulphone hydroxyapatite polymer has moderate number of pores and higher mechanical property, is nontoxic to stem cells, has osteogenic differentiation effect, and can replace hydroxyapatite to be used for preparing related instruments or materials for treating diseases such as bone injury and bone defect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a physical diagram of polysulfone hydroxyapatite polymer prepared in the example;
FIG. 2 is an SEM image of the polysulfone hydroxyapatite polymer prepared in comparative example 1 of the experimental example;
FIG. 3 is an enlarged view of FIG. 2;
FIG. 4 is an SEM image of the polysulfone hydroxyapatite polymer prepared in example 1 of the test example;
FIG. 5 is an enlarged view of FIG. 4;
FIG. 6 is an SEM image of a polysulfone hydroxyapatite polymer prepared in example 7 of the test example;
FIG. 7 is an enlarged view of FIG. 6;
FIG. 8 is a graph showing the effect of polysulfone hydroxyapatite polymer and hydroxyapatite on stem cell osteogenesis in a test example;
FIG. 9 is a graph showing cytotoxicity results of polysulfone hydroxyapatite polymer and hydroxyapatite in the test example.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The polysulfone hydroxyapatite polymer provided by the application and a preparation method and application thereof are specifically described below.
The application provides a preparation method of a polysulfone hydroxyapatite polymer, which comprises the following steps: the preparation raw materials of the polysulphone hydroxyapatite polymer are reacted at 1250-1350 ℃.
Every 100 parts of the preparation raw materials comprise 10-20 parts of polysulfone and 0.5-10 parts of hydroxyapatite, and the balance of N-methylpyrrolidone.
For reference, the amount of polysulfone contained in the above-mentioned preparation raw materials may be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts or the like per 100 parts, or may be any other value within the range of 10 to 20 parts.
The amount of hydroxyapatite contained in the above-mentioned preparation raw materials may be 0.5 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, etc., or may be any other value within a range of 0.5 to 10 parts, per 100 parts of the above-mentioned preparation raw materials.
In some exemplary embodiments, the above-described preparation materials may include 19.5 parts polysulfone, 0.5 parts hydroxyapatite, and 80 parts N-methylpyrrolidone per 100 parts of the preparation materials; alternatively, the preparation raw materials may include 19 parts of polysulfone, 1 part of hydroxyapatite and 80 parts of N-methylpyrrolidone per 100 parts of the above preparation raw materials; alternatively, the preparation raw materials may include 18 parts of polysulfone, 2 parts of hydroxyapatite and 80 parts of N-methylpyrrolidone per 100 parts of the above preparation raw materials; alternatively, the preparation raw materials may include 15 parts of polysulfone, 5 parts of hydroxyapatite and 80 parts of N-methylpyrrolidone per 100 parts of the preparation raw materials; alternatively, the preparation raw materials may include 10 parts of polysulfone, 10 parts of hydroxyapatite and 80 parts of N-methylpyrrolidone per 100 parts of the above preparation raw materials; alternatively, the preparation raw materials may include 20 parts of polysulfone, 5 parts of hydroxyapatite and 75 parts of N-methylpyrrolidone per 100 parts of the above preparation raw materials; alternatively, the preparation raw materials may include 20 parts of polysulfone, 10 parts of hydroxyapatite and 70 parts of N-methylpyrrolidone per 100 parts of the above preparation raw materials.
In some more typical embodiments, the polysulfone hydroxyapatite polymer is prepared from a polysulfone to hydroxyapatite mass ratio of 9:1 or 3:1. In some more typical embodiments, the polysulfone hydroxyapatite polymer is prepared from a mass ratio of polysulfone to hydroxyapatite of 3:1. The polysulphone hydroxyapatite polymer prepared by matching the mass ratio (especially 3:1) has higher tensile property and is more suitable for preparing orthopedic materials or instruments.
The Polysulfone (PSU) is an amorphous polymer with properties matching those of the flight metal. The main aromatic structure of the glass fiber has higher glass transition temperature and thermal degradation resistance. Polysulfone has the characteristics of high strength and rigidity, low creep rate, oxidation resistance, excellent hydrolysis resistance or molecular weight reduction, stability in water, inorganic acids, bases and salt solutions, biological inertness, and the like. The hydroxyapatite and polysulfone are reacted to generate the polymer, so that the obtained polymer has good biological performance and good mechanical performance.
The N-methyl pyrrolidone is mainly used as a supporting material to provide support in the polymerization process between polysulfone and hydroxyapatite to avoid collapse of the material, but it is noted that as the reaction proceeds, the N-methyl pyrrolidone volatilizes continuously and finally does not remain in the polysulfone hydroxyapatite polymer.
For reference, the hydroxyapatite used in the present application may be grade P81B HA, available from Plasma biological, UK, with a median size of about 7.32 μm. The hydroxyapatite with the particle size is favorable for being fully mixed with other components.
The polysulfone used in this application may be Ultrason S2010, commercially available from BSAF Plastics, germany, which has a medium viscosity, which facilitates extrusion.
In a specific operation, polysulfone particles may be ground into a powder, and the particle size of the ground polysulfone powder may be about 10 μm. Then mixing polysulfone powder, hydroxyapatite and N-methyl pyrrolidone according to a proportion to obtain a suspension; the suspension is injected into a mold (the shape of the mold is not limited and may be any shape) and the reaction is performed at 1250 to 1350 ℃.
As a reference, the reaction temperature of polysulfone powder, hydroxyapatite, and N-methylpyrrolidone may be 1250 ℃, 1260 ℃, 1270 ℃, 1280 ℃, 1290 ℃, 1300 ℃, 1310 ℃, 1320 ℃, 1330 ℃, 1340 ℃, 1350 ℃, or the like, or may be any other value within the range of 1250 to 1350 ℃.
If the reaction temperature is lower than 1250 ℃, the full reaction of the components is not facilitated; if the reaction temperature is higher than 1350 ℃, the polymer formation is not favored.
The reaction time of the polysulfone powder, the hydroxyapatite and the N-methylpyrrolidone may be 6 to 10 hours, such as 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours or 10 hours, and the like, and may be any other value within the range of 6 to 10 hours.
If the reaction time is shorter than 6 hours, the full reaction of each component is not facilitated; if the reaction time is longer than 10 hours, the polymer formation is not favored.
In some alternative embodiments, the temperature may be increased to 1250-1350 ℃ at a rate of 55-65 ℃/h. Illustratively, the heating rate may be 55 ℃/h, 56 ℃/h, 57 ℃/h, 58 ℃/h, 59 ℃/h, 60 ℃/h, 61 ℃/h, 62 ℃/h, 63 ℃/h, 64 ℃/h, 65 ℃/h, etc., as well as any other value within the range of 55-65 ℃/h.
If the temperature rising rate is too slow, the components are not favorable for full reaction; if the temperature rise rate is too high, the polymer formation is not favored.
After the reaction is finished, the temperature can be reduced to room temperature at the speed of 115-125 ℃/h. Illustratively, the cooling rate may be 115 ℃/h, 116 ℃/h, 117 ℃/h, 118 ℃/h, 119 ℃/h, 120 ℃/h, 121 ℃/h, 122 ℃/h, 123 ℃/h, 124 ℃/h, 125 ℃/h, or the like, as well as any other value within the range of 115-125 ℃/h.
If the cooling rate is too slow, the components are not favorable for full reaction; if the cooling rate is too fast, the polymer is not easy to form.
After the reaction, the N-methyl pyrrolidone in the prepared raw materials is volatilized, and basically no residue exists.
Correspondingly, the application also provides a polysulfone hydroxyapatite polymer prepared by the preparation method of any one of the previous embodiments.
The polysulfone hydroxyapatite polymer prepared by the method has a moderate number of pores, and the pore size is about 2-20 mu m. The polysulfone hydroxyapatite polymer also has higher tensile property, for example, the tensile capacity can reach 21.5MPa, and the defects that the hydroxyapatite in the raw material is fragile and not fatigue-resistant, and new bones formed in a porous hydroxyapatite network cannot bear mechanical load required by remodeling and the like are overcome. In addition, the polysulfone hydroxyapatite polymer is nontoxic to stem cells, has an osteogenic differentiation effect, and has high application value.
In addition, the application also provides application of the polysulfone hydroxyapatite polymer, which can be used for preparing orthopedic instruments or orthopedic materials.
Correspondingly, the application also provides a bone tissue engineering scaffold, the preparation raw materials of which comprise the polysulfone hydroxyapatite polymer, and the bone tissue engineering scaffold can be used for bone injury or bone defect and other aspects.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
This example provides a polysulfone hydroxyapatite polymer (as shown in figure 1) prepared by the following method:
grinding polysulfone particles into powder (particle size is about 10 μm), and mixing polysulfone powder, hydroxyapatite and N-methylpyrrolidone according to a mass ratio of 15:5:80 to obtain a suspension; the suspension is injected into a mould, heated to 1300 ℃ at a heating rate of 60 ℃/h and reacted for 8h, and then cooled to room temperature at a rate of 120 ℃/h.
Wherein polysulfone is Ultrason S2010, available from BSAF Plastics Germany, hydroxyapatite is grade P81B HA, available from Plasma Biotal, UK, with a bit size of about 7.32 μm.
Example 2
This embodiment differs from embodiment 1 in that: polysulfone powder, hydroxyapatite and N-methyl pyrrolidone are mixed according to the mass ratio of 19.5:0.5:80.
Example 3
This embodiment differs from embodiment 1 in that: polysulfone powder, hydroxyapatite and N-methyl pyrrolidone are mixed according to the mass ratio of 19:1:80.
Example 4
This embodiment differs from embodiment 1 in that: polysulfone powder, hydroxyapatite and N-methyl pyrrolidone are mixed according to the mass ratio of 18:2:80.
Example 5
This embodiment differs from embodiment 1 in that: polysulfone powder, hydroxyapatite and N-methyl pyrrolidone are mixed according to the mass ratio of 10:10:80.
Example 6
This embodiment differs from embodiment 1 in that: polysulfone powder, hydroxyapatite and N-methyl pyrrolidone are mixed according to the mass ratio of 20:5:75.
Example 7
This embodiment differs from embodiment 1 in that: polysulfone powder, hydroxyapatite and N-methyl pyrrolidone are mixed according to the mass ratio of 20:10:70.
Comparative example 1 (blank control group)
The difference between this comparative example and example 1 is that: polysulfone powder, hydroxyapatite and N-methyl pyrrolidone are mixed according to the mass ratio of 20:0:80.
Test examples
(1) Taking the polysulfone hydroxyapatite polymers prepared in example 1, example 7 and comparative example 1 as examples, the respective polymers were subjected to electron microscopy scanning, and the results are shown in fig. 2 to 7.
As can be seen from fig. 2 to 7: along with the continuous increase of the proportion of the hydroxyapatite, the pore space of the polysulfone hydroxyapatite copolymer is also continuously increased, and the increase of the pore space can improve the tensile property of the polymer to a certain extent; however, too many pores may lead to a significant decrease in tensile properties.
(2) The polysulfone hydroxyapatite polymer support stent forms prepared in examples 1 to 7 and comparative example 1 were referred to national standards of GB 9641-1988 and GB 8813-88, and tensile strength was performed using a universal tester, and the results are shown in Table 1.
Table 1 test results
As can be seen from table 1, the polysulfone hydroxyapatite polymer provided in the examples of the present application has certain mechanical properties.
(3) Taking example 1 as an example, the obtained polysulfone hydroxyapatite polymer was prepared into a scaffold, and the stem cell osteogenesis was studied using the scaffold made of hydroxyapatite as a control.
The experimental method comprises the following steps: ultraviolet sterilized hydroxyapatite scaffold and polysulfone hydroxyapatite polymer scaffold were placed in 24-well plate, and umbilical blood stem cells were then seeded on the surface (2×10) 4 Well), the original culture broth was discarded after 3 days of culture in an incubator, washed 3 times with PBS, then 0.25% pancreatin was added for digestion, the cells were collected, washed 3 times with PBS, the cell lysate was added, and alkaline phosphatase and osteocalcin activities were calculated according to ELISA kit instructions.
The results are shown in fig. 8, and as can be seen from fig. 8: polysulfone hydroxyapatite polymer and hydroxyapatite have little effect on promoting stem cell osteogenesis.
(4) Taking example 1 as an example, the obtained polysulfone hydroxyapatite polymer was prepared into a scaffold, which was subjected to cytotoxicity detection, and the scaffold made of hydroxyapatite was used as a control.
The experimental method comprises the following steps: placing ultraviolet sterilized hydroxyapatite and polysulfone hydroxyapatite polymer scaffold into 24-well plate, and planting umbilical blood stem cells on its surface (2×10) 4 Well), 3 days, 6 days and 9 days, cytotoxicity was detected with MTT.
The result is shown in fig. 9, and as can be seen from fig. 9: polysulfone hydroxyapatite polymer is not significantly different from hydroxyapatite in the effect on cell viability.
On the above, it can be seen from the above experiments that the polysulfone hydroxyapatite polymer formed by polysulfone and hydroxyapatite in a mass ratio of 3:1 has more pores and higher tensile properties than hydroxyapatite; the difference between the polysulfone hydroxyapatite polymer and the hydroxyapatite is not obvious in the aspects of inducing stem cell osteogenesis and influencing cell viability, so that the polysulfone hydroxyapatite polymer provided by the application can be used for preparing products such as scaffolds for treating diseases such as bone injury and bone defect, and the like by replacing the hydroxyapatite.
In summary, the preparation method of the polysulfone hydroxyapatite polymer provided by the application is simple and easy to operate, and the prepared polysulfone hydroxyapatite polymer has more pores and higher strength and mechanical property and can be used for preparing related materials or devices for treating diseases such as bone injury and bone defect instead of hydroxyapatite.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The preparation method of the polysulfone hydroxyapatite polymer is characterized by comprising the following steps:
reacting the preparation raw materials of the polysulfone hydroxyapatite polymer at 1250-1350 ℃;
each 100 parts of the preparation raw materials comprise 10-20 parts of polysulfone and 0.5-10 parts of hydroxyapatite, and the balance of N-methylpyrrolidone;
raising the temperature to 1250-1350 ℃ at the speed of 55-65 ℃/h, and reacting for 6-10h; after the reaction, cooling to room temperature at a speed of 115-125 ℃/h;
the mass ratio of the polysulfone to the hydroxyapatite is 9:1 or 3:1.
2. The method of claim 1, wherein the mass ratio of polysulfone to hydroxyapatite is 3:1.
3. The method of claim 1 or 2, wherein the hydroxyapatite is P81B grade HA; and/or, the polysulfone is Ultrason S2010.
4. A polysulfone hydroxyapatite polymer prepared by the method of any one of claims 1 to 3.
5. Use of the polysulfone hydroxyapatite polymer of claim 4 for the preparation of an orthopaedic device or an orthopaedic material.
6. A bone tissue engineering scaffold, characterized in that the preparation raw material of the bone tissue engineering scaffold comprises the polysulfone hydroxyapatite polymer according to claim 4.
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