CN101274108B - Compound porous bracket and method of producing the same - Google Patents
Compound porous bracket and method of producing the same Download PDFInfo
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- CN101274108B CN101274108B CN2008100972169A CN200810097216A CN101274108B CN 101274108 B CN101274108 B CN 101274108B CN 2008100972169 A CN2008100972169 A CN 2008100972169A CN 200810097216 A CN200810097216 A CN 200810097216A CN 101274108 B CN101274108 B CN 101274108B
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- 238000000034 method Methods 0.000 title claims description 18
- 150000001875 compounds Chemical class 0.000 title description 2
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- 238000002360 preparation method Methods 0.000 claims abstract description 38
- 238000001035 drying Methods 0.000 claims abstract description 36
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 34
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- 229910052586 apatite Inorganic materials 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 33
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 claims abstract description 28
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- 239000011148 porous material Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
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- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 9
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
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- 239000012528 membrane Substances 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- NLVFBUXFDBBNBW-PBSUHMDJSA-N tobramycin Chemical compound N[C@@H]1C[C@H](O)[C@@H](CN)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O[C@@H]2[C@@H]([C@@H](N)[C@H](O)[C@@H](CO)O2)O)[C@H](N)C[C@@H]1N NLVFBUXFDBBNBW-PBSUHMDJSA-N 0.000 claims description 5
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- 238000004513 sizing Methods 0.000 abstract 4
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 3
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
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- Materials For Medical Uses (AREA)
Abstract
The invention relates to a composite porous scaffold and a preparation method thereof, in particular to a composite porous scaffold combining calcium sulfate and apatite compound and a preparation method thereof, and pertains to the technical field of medical apparatus and instruments. Composite sizing material combining calcium sulfate hemihydrate powder and crushed apatite compound is first prepared; calcium sulfate sizing material is evenly brushed on polyurethane foam to obtain a porous calcium sulfate ceramic scaffold after the steps of drying and high-temperature treatment. The obtained porous calcium sulfate ceramic scaffold is then immersed in the composite sizing material and then placed indoors for natural drying after the treatment of sizing hanging and finally heated and dried to obtain the composite porous scaffold combining calcium sulfate and apatite compound of the invention.
Description
Technical Field
The invention relates to a composite porous scaffold and a preparation method thereof, in particular to a composite porous scaffold of a calcium sulfate and apatite compound and a preparation method thereof. Belongs to the technical field of medical appliances.
Background
Bone loss due to trauma, infection, tumor, etc. results in the formation of large gaps called bone defects. Most bone defects are difficult to heal and eventually form bone nonunions. Because of the large defect gap, osteoblasts are difficult to climb through the gap and normal healing processes cannot take place, being filled only by fibrous tissue. The treatment of bone defects is a difficult and challenging subject in the orthopedic field, and a certain treatment aim is achieved mainly through autologous or allogeneic tissue transplantation and biological replacement materials clinically. Currently, the most common autologous tissue transplantation has limited clinical application due to unfavorable factors such as insufficient sources, large wounds, donor-area complications and the like; the allogeneic tissue transplantation has the factors of xenogenic rejection reaction, limited source, risk of disease transmission and the like; therefore, it is a goal of the clinical workers to find a substitute which does not damage themselves and can achieve the functional effects of the intended bone defect repair. The tissue engineering technology provides a new idea and a new method for solving the problem.
The basic method of tissue engineering is: the high-concentration tissue cells cultured in vitro are expanded and adsorbed on a tissue engineering scaffold material which has good biocompatibility and can be degraded and absorbed by human bodies, the material has the functions of providing living space for the cells, enabling the cells to obtain enough nutrient substances, carrying out gas exchange, enabling the cells to grow according to a prefabricated three-dimensional scaffold, then implanting a complex of the cells and the biological material into a damaged part of an organism, and continuously proliferating and propagating the implanted cells in the degradation and absorption process of the biological scaffold to form new corresponding tissues and organs with original special functions and forms so as to achieve the purposes of repairing wounds and reconstructing functions.
Bone tissue engineering is an important branch of tissue engineering and is expected to be applied in clinic first. At present, more complete theoretical and technical routes for constructing seed cells, cell carrier scaffolds and tissues are gradually formed. It is undeniable that these efforts are a certain distance away from the ultimate clinical application of bone tissue engineering. Therefore, the research focus at the present stage is still focused on finding suitable seed cells, materials and in-vivo construction modes, finding the optimal combination of the seed cells, the materials and the in-vivo construction modes, simulating the natural process of human bone repair, and reproducing the bone structure and functions to the maximum extent. At present, the hot spot of the bone tissue engineering research focuses on seed cells, scaffold materials and bioactive factors. The scaffold material has the function of providing a porous material as a tissue regeneration framework, cells cultured in vitro are planted on the porous material and are implanted back into the body to guide the continuous growth of required tissues, and meanwhile, the framework material gradually disappears, and finally, completely living tissues are formed and regenerated in an original framework area to realize permanent repair.
The ideal scaffold material needs to meet the following conditions (1) that the surface structure and properties of the material are favorable for cell adsorption, proliferation and differentiation; (2) degrading at a controllable speed; (3) good biocompatibility; (4) the material is easy to be made into three-dimensional porous shape and irregular geometric shape; (5) has a certain mechanical strength to support physiological pressure; (6) can maintain the differentiation of cells without causing the variation of the cells. At present, the preparation method and process of the porous scaffold material for bone tissue engineering are basically mature in China, and the adopted scaffold materials mainly comprise artificially synthesized materials, natural biological derived materials and composite materials, wherein the materials are commonly used such as polyglycolic Acid (PGA), polylactic Acid (PLA), tricalcium phosphate (TCP), Hydroxyapatite (HA) and the like. Through intensive research, the materials have defects of biodegradability and osteogenesis in the further research process; although PGA and PLA have good biocompatibility, degradability and absorbability, the PGA and PLA have the defects of high cost, poor plasticity and the like, and the degraded acidic metabolite can reduce the pH value around the polymer, influence the growth of cells and tissues, and also cause fibrosis and immunoreaction of surrounding tissues. HA is difficult to absorb and replace after being implanted, stays in vivo for a long time and prevents reconstruction and complete repair of bone tissues and the like, so that the thought is not widened to find a new material, namely Medical-grade Calcium Sulfate (Medical-grade Calcium Sulfate), which HAs good biocompatibility, degradability and osteogenesis effect, and can obtain good effect and application value when used as a raw material for preparing a stent.
Disclosure of Invention
The purpose of the invention is as follows: the invention discloses a composite porous scaffold of a calcium sulfate and apatite compound and a preparation method thereof.
Through various researches, calcium sulfate is a bone guiding material, mainly used as a filler of a gap, and can restore the shape and contour of bones and prevent soft tissue from growing in. It provides an osteoconductive matrix for vascular and osteoblast ingrowth.
A preparation method of a composite porous scaffold of calcium sulfate and apatite compound comprises the following steps:
1) preparing composite slurry of semi-hydrated calcium sulfate powder and ground apatite compound;
2) uniformly coating the calcium sulfate slurry on polyurethane foam, and drying and performing high-temperature treatment to obtain a calcium sulfate ceramic porous support;
3) and soaking the calcium sulfate ceramic porous support in the composite slurry for slurry hanging, placing the support in an indoor environment for natural drying, and then heating and drying to obtain the composite porous support of the calcium sulfate and apatite composite.
The preparation method of the composite slurry comprises the following steps: mixing calcium sulfate hemihydrate powder with ground apatite compound, mixing calcium sulfate powder, apatite compound powder and tobramycin powder in the ratio of 1.5-2.5 to 0.8-1.2, preferably 2 to 1, and adding 0.5-2%, preferably 1% of carboxymethyl cellulose rheological agent and 25-45%, preferably 35% of deionized water to obtain the composite slurry.
The composition and preparation method of the apatite compound are as follows: apatite was mixed with collagen in a ratio of 3: 2.
The polyurethane foam is as follows: 45ppi polyurethane foam has a pore diameter of 150-500 μm and a porosity of 84.29%, and has high elasticity, uniform pores, high porosity, and three-dimensional network structure.
The treatment method of the polyurethane foam comprises the following steps: cutting the foam into cylindrical small blocks of phi 5mm multiplied by 15mm, washing with distilled water, immersing in 10% sodium hydroxide solution, hydrolyzing at 60 deg.C for 4h to remove the internetwork membrane in the foam, repeatedly kneading, washing with clear water, and air drying for use.
The preparation method of the calcium sulfate slurry comprises the following steps: adding 10-50% (preferably 15%) of silica sol binder and 20-60% (preferably 40%) of deionized water into the calcium sulfate powder, and fully and uniformly mixing to obtain the calcium sulfate slurry.
The preparation method of the calcium sulfate hemihydrate comprises the following steps: mixing calcium sulfate dihydrate powder with deionized water, placing the mixture in a closed pressure container, adding a conventional amount of polyacrylamide crystal transformation agent, dissolving and recrystallizing the calcium sulfate dihydrate at 90-160 ℃ and 1.5-4.5 atmospheric pressures to form a crystal variant of calcium sulfate hemihydrate, quickly taking out the crystal variant, physically filtering, placing the crystal variant into an air drying oven, drying the crystal variant at the constant temperature of 140-160 ℃ for 4-6 hours, and grinding and sieving to prepare the calcium sulfate hemihydrate crystal.
The polyacrylamide is coated on the surface of the polyurethane foam to form a polymer layer, so that the adhesion among the polyurethane foams is enhanced.
The method of the step 2) is as follows: soaking cut phi-5 mm x 15mm polyurethane foam cylinder small blocks in calcium sulfate slurry, taking out after all pores and stems on the polyurethane foam are uniformly adhered with the calcium sulfate slurry to prepare a calcium sulfate blank, naturally drying the blank for 24 hours in an indoor environment, and drying for 24 hours in an electrothermal blowing drying oven at 110 ℃; the combustion volatilization of the polyurethane foam is the key point of the forming of the ceramic porous bracket, the plastic-removing temperature is about 300 ℃ according to the determination of an organic foam GH-1GI curve, the temperature rising speed is controlled at 1 ℃/min when a green body is sintered at 300 to 600 ℃, and thus the green body is prevented from being damaged by gas generated by the oxidation of the organic foam; and then raising the temperature to 1000 ℃ and preserving the temperature for 2h, then cooling along with the furnace temperature, completely decomposing and volatilizing the polyurethane at high temperature, and successfully preparing the calcium sulfate ceramic porous support.
The method of the step 3) is as follows: after being soaked in the composite slurry for further slurry hanging, the calcium sulfate ceramic porous support is placed in an indoor environment for natural drying for 10-40 hours (preferably 24 hours), and is dried for 5-20 hours (preferably 12 hours) at 80 ℃; after the step is repeated for 3-5 times, all the pore walls of the calcium sulfate ceramic porous scaffold are uniformly adhered with the composite material, and the preparation of the composite biological porous scaffold of the calcium sulfate and apatite composite is finished. Sterilizing by cobalt-60 irradiation, and storing under sterile condition.
Advantageous effects
After scanning, an electron microscope SEM topography can be detected, the aperture of the obtained composite bracket is distributed between 150-300 mu m, the holes are communicated with each other, and micropores in the material are rich and uniformly distributed, so that the material has a loose coral-shaped structure. This structure is similar to the cancellous bone framework of a living organism, which facilitates the ingrowth of bone tissue and the biodegradation of the material itself.
Through test calculation, the average porosity of the porous scaffold is 62.59-79.36%, and the compressive strength is 27-53MPa (the biomechanical strength of the normal human bone tissue is 7.09MPa, and the dense bone is 177-.
When calcium sulfate is absorbed, the new bone shapes and restores anatomical features and structural characteristics. Its most important advantage is that its natural resorption rate is comparable to the rate of new bone formation. With the absorption of the medical calcium sulfate implant, the new bone gradually recovers the anatomical properties and structural features.
Detailed Description
Example 1
Preparation of raw materials: (1) calcium sulfate is a common industrial raw material, has wide sources and very low cost, and can be divided into 3 types on the chemical property: ordinary calcium sulfate (calcium sulfate dihydrate), anhydrous calcium sulfate, and calcium sulfate hemihydrate; the latter is formed by deep processing of calcium sulfate dihydrate, the crystal structure of the calcium sulfate hemihydrate is uniform, the purity is high, and the calcium sulfate hemihydrate can be used for research and treatment in the field of medical orthopedics, and is also called as medical calcium sulfate; the specific preparation method comprises the following steps: the preparation method of the calcium sulfate hemihydrate comprises the following steps: mixing calcium sulfate dihydrate powder with deionized water, placing the mixture in a closed pressure container, adding a conventional amount of polyacrylamide crystal transformation agent, dissolving and recrystallizing the calcium sulfate dihydrate at 160 ℃ and 1.5 atmospheric pressures to form a crystal variant of the calcium sulfate hemihydrate, quickly taking out the crystal variant, carrying out physical filtration, placing the crystal variant in an air drying oven, drying the crystal variant at the constant temperature of 160 ℃ for 4 hours, and grinding and sieving the crystal variant to prepare the calcium sulfate hemihydrate. (2) Freezing the apatite compound to-70 deg.C, and further cooling in vacuum until the residual water content is reduced to below 5%. (3) A silica sol binder, a carboxymethyl cellulose rheological agent, a polyurethane foam, a QM21SP2 ball mill, a 101A-3E electric hot blast drying oven, a R23-115-12 box-type resistance furnace, and the like were prepared.
The preparation process of the composite material comprises the following steps:
a. early preparation work: (1) respectively putting the blocks of the calcium sulfate and apatite compound into a ball mill, and ball-milling for 1h to obtain powder; (2) adding 15% of silica sol binder and 40% of deionized water into the calcium sulfate powder, and fully and uniformly mixing to obtain MSC slurry; (3) putting calcium sulfate powder, apatite compound powder and tobramycin powder in a ratio of 2: 1, 1% carboxymethyl cellulose rheological agent and 35% deionized water into a ball milling tank, and ball milling for 1h to obtain uniformly dispersed composite slurry; (4) the experiment selects 45ppi polyurethane foam, the aperture is between the proportion of 150-500 mu m and the porosity of 84.29%, the elasticity is high, the pores are uniform, the porosity is high, and the polyurethane foam has a three-dimensional network structure. Cutting the foam into cylindrical small blocks with the diameter of 5mm multiplied by 15mm required by the experiment, cleaning the small blocks by distilled water, immersing the small blocks into a sodium hydroxide solution with the concentration of 10 percent, hydrolyzing the small blocks at the temperature of 60 ℃ for 4 hours, removing the internetwork membrane in the foam, repeatedly kneading the small blocks, washing the small blocks by clear water, and airing the small blocks for later use. In order to improve the adhesion between the organic foam and the slurry, polyacrylamide is coated on the surface of the organic foam to form a polymer layer, thereby enhancing the adhesion between the organic foam.
b. The process flow comprises the following steps:
(1) soaking the cut polyurethane foam cylinder small blocks with the diameter of 5mm multiplied by 15mm in calcium sulfate slurry, taking out after all pores and stems on the polyurethane foam are uniformly adhered with the calcium sulfate slurry to prepare a calcium sulfate blank, then naturally drying the blank for 24 hours in an indoor environment, and drying for 24 hours in an electrothermal blowing drying oven at the temperature of 110 ℃; the combustion volatilization of the polyurethane foam is the key point of the forming of the ceramic porous bracket, the plastic-removing temperature is about 300 ℃ according to the determination of an organic foam GH-1GI curve, the temperature rising speed is controlled at 1 ℃/min when a green body is sintered at 300 to 600 ℃, and thus the green body is prevented from being damaged by gas generated by the oxidation of the organic foam; and then raising the temperature to 1000 ℃ and preserving the temperature for 2h, then cooling along with the furnace temperature, completely decomposing and volatilizing the polyurethane at high temperature, and successfully preparing the calcium sulfate ceramic porous support.
(2) After being soaked in the composite slurry for further slurry hanging, the calcium sulfate ceramic porous support is placed in an indoor environment for natural drying for 10 hours and dried for 5 hours in an electrothermal blowing drying oven at the temperature of 80 ℃; after the step is repeated for 3 times, all the pore walls of the calcium sulfate ceramic porous scaffold are uniformly adhered with the composite material, and the preparation of the composite biological porous scaffold of the calcium sulfate/apatite composite is completed. Sterilizing by cobalt-60 irradiation, and storing under sterile condition.
Example 2
Preparation of raw materials: (1) calcium sulfate is a common industrial raw material, has wide sources and very low cost, and can be divided into 3 types on the chemical property: ordinary calcium sulfate (calcium sulfate dihydrate), anhydrous calcium sulfate, and calcium sulfate hemihydrate; the latter is formed by deep processing of calcium sulfate dihydrate, the crystal structure of the calcium sulfate hemihydrate is uniform, the purity is high, and the calcium sulfate hemihydrate can be used for research and treatment in the field of medical orthopedics, and is also called as medical calcium sulfate; the specific preparation method comprises the following steps: the preparation method of the calcium sulfate hemihydrate comprises the following steps: mixing calcium sulfate dihydrate powder with deionized water, placing the mixture in a closed pressure container, adding a conventional amount of polyacrylamide crystal transformation agent, dissolving and recrystallizing the calcium sulfate dihydrate at 90 ℃ and 4.5 atmospheric pressures to form a crystal variant of calcium sulfate hemihydrate, quickly taking out the crystal variant, carrying out physical filtration, placing the crystal variant in an air drying oven, drying the crystal variant at the constant temperature of 140 ℃ for 6 hours, and grinding and sieving the crystal variant to prepare the calcium sulfate hemihydrate. (2) Freezing the apatite compound to-100 deg.C, and further cooling in vacuum until the residual water content is reduced to below 5%. (3) A silica sol binder, a carboxymethyl cellulose rheological agent, a polyurethane foam, a QM21SP2 ball mill, a 101A-3E electric hot blast drying oven, a R23-115-12 box-type resistance furnace, and the like were prepared.
The preparation process of the composite material comprises the following steps:
a. early preparation work: (1) respectively putting the blocks of the calcium sulfate and apatite compound into a ball mill, and ball-milling for 1h to obtain powder; (2) adding 50% of silica sol binder and 60% of deionized water by weight into the calcium sulfate powder, and fully and uniformly mixing to obtain MSC slurry; (3) putting calcium sulfate powder, apatite compound powder and tobramycin powder in a ratio of 2.5: 0.8, 2% of carboxymethyl cellulose rheological agent and 45% of deionized water into a ball milling tank, and ball milling for 1h to obtain uniformly dispersed composite slurry; (4) the experiment selects 45ppi polyurethane foam, the aperture is between the proportion of 150-500 mu m and the porosity of 84.29%, the elasticity is high, the pores are uniform, the porosity is high, and the polyurethane foam has a three-dimensional network structure. Cutting the foam into cylindrical small blocks with the diameter of 5mm multiplied by 15mm required by the experiment, cleaning the small blocks by distilled water, immersing the small blocks into a sodium hydroxide solution with the concentration of 10 percent, hydrolyzing the small blocks at the temperature of 60 ℃ for 4 hours, removing the internetwork membrane in the foam, repeatedly kneading the small blocks, washing the small blocks by clear water, and airing the small blocks for later use. In order to improve the adhesion between the organic foam and the slurry, polyacrylamide is coated on the surface of the organic foam to form a polymer layer, thereby enhancing the adhesion between the organic foam.
b. The process flow comprises the following steps:
(1) soaking the cut polyurethane foam cylinder small blocks with the diameter of 5mm multiplied by 15mm in calcium sulfate slurry, taking out after all pores and stems on the polyurethane foam are uniformly adhered with the calcium sulfate slurry to prepare a calcium sulfate blank, then naturally drying the blank for 24 hours in an indoor environment, and drying for 24 hours in an electrothermal blowing drying oven at the temperature of 110 ℃; the combustion volatilization of the polyurethane foam is the key point of the forming of the ceramic porous bracket, the plastic-removing temperature is about 300 ℃ according to the determination of an organic foam GH-1GI curve, the temperature rising speed is controlled at 1 ℃/min when a green body is sintered at 300 to 600 ℃, and thus the green body is prevented from being damaged by gas generated by the oxidation of the organic foam; and then raising the temperature to 1000 ℃ and preserving the temperature for 2h, then cooling along with the furnace temperature, completely decomposing and volatilizing the polyurethane at high temperature, and successfully preparing the calcium sulfate ceramic porous support.
(2) After being soaked in the composite slurry for further slurry hanging, the calcium sulfate ceramic porous support is placed in an indoor environment for natural drying for 40 hours, and is dried in an electric heating air blast drying oven for 20 hours at the temperature of 80 ℃; after the step is repeated for 5 times, all the pore walls of the calcium sulfate ceramic porous scaffold are uniformly adhered with the composite material, and the preparation of the composite biological porous scaffold of the calcium sulfate/apatite composite is completed. Sterilizing by cobalt-60 irradiation, and storing under sterile condition.
Example 3
Preparation of raw materials: (1) calcium sulfate is a common industrial raw material, has wide sources and very low cost, and can be divided into 3 types on the chemical property: ordinary calcium sulfate (calcium sulfate dihydrate), anhydrous calcium sulfate, and calcium sulfate hemihydrate; the latter is formed by deep processing of calcium sulfate dihydrate, the crystal structure of the calcium sulfate hemihydrate is uniform, the purity is high, and the calcium sulfate hemihydrate can be used for research and treatment in the field of medical orthopedics, and is also called as medical calcium sulfate; the specific preparation method comprises the following steps: the preparation method of the calcium sulfate hemihydrate comprises the following steps: mixing calcium sulfate dihydrate powder with deionized water, placing the mixture in a closed pressure container, adding a conventional amount of polyacrylamide crystal transformation agent, dissolving and recrystallizing the calcium sulfate dihydrate at 150 ℃ and 2 atmospheric pressures to form a crystal variant of calcium sulfate hemihydrate, quickly taking out the crystal variant, carrying out physical filtration, placing the crystal variant in an air-blast drying oven, drying the crystal variant at the constant temperature of 150 ℃ for 4.5 hours, and grinding and sieving the crystal variant to prepare the calcium sulfate hemihydrate. (2) Freezing the apatite compound to-90 deg.C, and further cooling in vacuum until the residual water content is reduced to below 5%. (3) A silica sol binder, a carboxymethyl cellulose rheological agent, a polyurethane foam, a QM21SP2 ball mill, a 101A-3E electric hot blast drying oven, a R23-115-12 box-type resistance furnace, and the like were prepared.
The preparation process of the composite material comprises the following steps:
a. early preparation work: (1) respectively putting the blocks of the calcium sulfate and apatite compound into a ball mill, and ball-milling for 1h to obtain powder; (2) adding 15% of silica sol binder and 40% of deionized water into the calcium sulfate powder, and fully and uniformly mixing to obtain MSC slurry; (3) calcium sulfate powder, apatite compound powder and tobramycin powder in the ratio of 1.5 to 1.2, 0.5% carboxymethyl cellulose rheological agent and 35% deionized water are put into a ball milling tank and ball milled for 1 hour to obtain uniformly dispersed compound slurry; (4) the experiment selects 45ppi polyurethane foam, the aperture is between the proportion of 150-500 mu m and the porosity of 84.29%, the elasticity is high, the pores are uniform, the porosity is high, and the polyurethane foam has a three-dimensional network structure. Cutting the foam into cylindrical small blocks with the diameter of 5mm multiplied by 15mm required by the experiment, cleaning the small blocks by distilled water, immersing the small blocks into a sodium hydroxide solution with the concentration of 10 percent, hydrolyzing the small blocks at the temperature of 60 ℃ for 4 hours, removing the internetwork membrane in the foam, repeatedly kneading the small blocks, washing the small blocks by clear water, and airing the small blocks for later use. In order to improve the adhesion between the organic foam and the slurry, polyacrylamide is coated on the surface of the organic foam to form a polymer layer, thereby enhancing the adhesion between the organic foam.
b. The process flow comprises the following steps:
(1) soaking the cut polyurethane foam cylinder small blocks with the diameter of 5mm multiplied by 15mm in calcium sulfate slurry, taking out after all pores and stems on the polyurethane foam are uniformly adhered with the calcium sulfate slurry to prepare a calcium sulfate blank, then naturally drying the blank for 24 hours in an indoor environment, and drying for 24 hours in an electrothermal blowing drying oven at the temperature of 110 ℃; the combustion volatilization of the polyurethane foam is the key point of the forming of the ceramic porous bracket, the plastic-removing temperature is about 300 ℃ according to the determination of an organic foam GH-1GI curve, the temperature rising speed is controlled at 1 ℃/min when a green body is sintered at 300 to 600 ℃, and thus the green body is prevented from being damaged by gas generated by the oxidation of the organic foam; and then raising the temperature to 1000 ℃ and preserving the temperature for 2h, then cooling along with the furnace temperature, completely decomposing and volatilizing the polyurethane at high temperature, and successfully preparing the calcium sulfate ceramic porous support.
(2) After being soaked in the composite slurry for further slurry hanging, the calcium sulfate ceramic porous support is placed in an indoor environment for natural drying for 30 hours and dried for 15 hours in an electrothermal blowing drying oven at the temperature of 80 ℃; after the step is repeated for 3 times, all the pore walls of the calcium sulfate ceramic porous scaffold are uniformly adhered with the composite material, and the preparation of the composite biological porous scaffold of the calcium sulfate/apatite composite is completed. Sterilizing by cobalt-60 irradiation, and storing under sterile condition.
After scanning, an electron microscope SEM topography can be detected, the aperture of the obtained composite bracket is distributed between 150-300 mu m, the holes are communicated with each other, and micropores in the material are rich and uniformly distributed, so that the material has a loose coral-shaped structure. This structure is similar to the cancellous bone framework of a living organism, which facilitates the ingrowth of bone tissue and the biodegradation of the material itself.
Through test calculation, the average porosity of the porous scaffold is 62.59-79.36%, and the compressive strength is 27-53MPa (the biomechanical strength of the normal human bone tissue is 7.09MPa, and the dense bone is 177-.
When calcium sulfate is absorbed, the new bone shapes and restores anatomical features and structural characteristics. Its most important advantage is that its natural resorption rate is comparable to the rate of new bone formation. With the absorption of the medical calcium sulfate implant, the new bone gradually recovers the anatomical properties and structural features.
Claims (5)
1. A preparation method of a composite porous scaffold of calcium sulfate and apatite compound is characterized by comprising the following steps: the preparation method comprises the following steps:
1) preparing composite slurry of semi-hydrated calcium sulfate powder and ground apatite compound;
2) uniformly coating the calcium sulfate slurry on polyurethane foam, and drying and performing high-temperature treatment to obtain a calcium sulfate ceramic porous support;
3) soaking the calcium sulfate ceramic porous support in the composite slurry for slurry hanging, placing the composite slurry in an indoor environment for natural drying, and then heating and drying to obtain a composite porous support of a calcium sulfate and apatite composite;
wherein,
the preparation method of the composite slurry comprises the following steps: mixing calcium sulfate hemihydrate powder with ground apatite compound, mixing calcium sulfate powder, apatite compound powder and tobramycin powder in the ratio of 1.5-2.5 to 0.8-1.2, adding 0.5-2% carboxymethyl cellulose rheological agent and 25-45% deionized water and mixing to obtain composite slurry;
the preparation method of the apatite compound comprises the following steps: mixing apatite and collagen at a ratio of 3: 2;
the polyurethane foam is treated by the following method: cutting the foam into cylindrical small blocks of phi 5mm multiplied by 15mm, cleaning the cylindrical small blocks with distilled water, immersing the cylindrical small blocks into a 10% sodium hydroxide solution, hydrolyzing the cylindrical small blocks at the temperature of 60 ℃ for 4 hours, removing the internetwork membrane in the foam, repeatedly kneading the cylindrical small blocks, washing the cylindrical small blocks with clear water, and airing the cylindrical small blocks for later use; the preparation method of the calcium sulfate slurry comprises the following steps: adding 10-50% of silica sol binder and 20-60% of deionized water into the calcium sulfate powder, and fully and uniformly mixing to obtain the calcium sulfate slurry.
2. The method of claim 1, wherein: the polyurethane foam is as follows: the 45ppi polyurethane foam has the pore diameter of 150-500 mu m and the porosity of 84.29 percent, high elasticity, uniform pores and high porosity and has a three-dimensional network structure.
3. The method of claim 1, wherein: the preparation method of the calcium sulfate hemihydrate comprises the following steps: mixing calcium sulfate dihydrate powder with deionized water, placing the mixture in a closed pressure container, adding a conventional amount of polyacrylamide crystal transformation agent, dissolving and recrystallizing the calcium sulfate dihydrate at 90-160 ℃ and 1.5-4.5 atmospheric pressures to form a crystal variant of calcium sulfate hemihydrate, quickly taking out the crystal variant, carrying out physical filtration, placing the crystal variant into an air drying oven, drying the crystal variant at constant temperature of 140-160 ℃ for 4-6 hours, and grinding and sieving the crystal variant to prepare the calcium sulfate hemihydrate.
4. The method of claim 1, wherein: the polyacrylamide is coated on the surface of the polyurethane foam to form a polymer layer, so that the adhesion among the polyurethane foams is enhanced.
5. The method of claim 1, wherein: the method of the step 3) is as follows: after being soaked in the composite slurry for further slurry hanging, the calcium sulfate ceramic porous support is naturally dried for 10 to 40 hours in an indoor environment and is dried for 5 to 20 hours at the temperature of 80 ℃; after repeating the steps for 3-5 times, the composite material is uniformly adhered to all the pore walls of the calcium sulfate ceramic porous support, and at the moment, the composite biological porous support of the calcium sulfate and apatite composite is prepared, and is sterilized by cobalt-60 irradiation and then is aseptically stored for later use.
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| CN110636869A (en) * | 2017-03-14 | 2019-12-31 | 段维新 | Method for free forming bone substitute and composite material used therefor |
| ES2893203T3 (en) * | 2017-10-06 | 2022-02-08 | Dsm Ip Assets Bv | Method for making an osteoconductive fibrous article and a medical implant comprising this osteoconductive fibrous article |
| EP3691701B8 (en) | 2017-10-06 | 2021-12-22 | DSM IP Assets B.V. | Method of making an osteoconductive polymer article and an osteoconductive polymer article thus made |
| CN107952110A (en) * | 2017-11-27 | 2018-04-24 | 山东明德生物医学工程有限公司 | A kind of filling material of bone and preparation method |
| CN111345851B (en) * | 2020-03-13 | 2021-12-17 | 辽宁石油化工大学 | Method for ultrasonic evaluation of biological porous material to guide tissue repair process |
| CN112479735A (en) * | 2020-12-08 | 2021-03-12 | 昆明市延安医院 | CaSO-containing food4beta-TCP composite ceramic material, preparation method and application |
| CN117229561B (en) * | 2023-11-10 | 2024-02-06 | 中裕软管科技股份有限公司 | Polyurethane toughening modified multifunctional composite material with porous structure and preparation method thereof |
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