CN115192777B - Degradable hydroxyapatite/levorotatory polylactic acid alveolar bone implant and preparation method thereof - Google Patents
Degradable hydroxyapatite/levorotatory polylactic acid alveolar bone implant and preparation method thereof Download PDFInfo
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- CN115192777B CN115192777B CN202210831391.6A CN202210831391A CN115192777B CN 115192777 B CN115192777 B CN 115192777B CN 202210831391 A CN202210831391 A CN 202210831391A CN 115192777 B CN115192777 B CN 115192777B
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- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 76
- 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 title claims abstract description 76
- 239000007943 implant Substances 0.000 title claims abstract description 64
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Classifications
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/54—Biologically active materials, e.g. therapeutic substances
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- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
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- A—HUMAN NECESSITIES
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Abstract
The invention discloses a degradable hydroxyapatite/levorotatory polylactic acid alveolar bone implant which is prepared by melting and forming hydroxyapatite/levorotatory polylactic acid composite powder through a laser selective area, wherein the hydroxyapatite/levorotatory polylactic acid composite powder comprises hydroxyapatite and levorotatory polylactic acid. The preparation method of the invention comprises the following steps: the hydroxyapatite/levorotatory polylactic acid composite powder treated by ball milling, extrusion granulation, crushing into powder and spheroidization process is placed in a laser selective area for melting, and is printed layer by layer to generate the personalized alveolar bone implant, so that the anatomical shape of the alveolar bone can be closely attached. The implant has good biocompatibility and mechanical strength, can be naturally degraded after being implanted into a dental bed, and can easily absorb and utilize calcium and phosphorus released by degradation by tissues so as to induce bone cell generation; meanwhile, the hydroxyapatite can be combined with cell membranes through hydrogen bonds, so that the bonding of the implant and surrounding normal tissues is promoted, and the difficult problem that the current alveolar bone is difficult to repair and regenerate due to insufficient bone quantity and different defect forms is solved.
Description
Technical Field
The invention belongs to the technical field of biological materials, and particularly relates to a degradable hydroxyapatite/levorotatory polylactic acid alveolar bone implant and a preparation method thereof.
Background
Alveolar bone defects can lead to serious deficiency of peripheral bone mass, cause deficiency of peripheral supporting tissues, even affect tooth embryos, cause changes of tooth morphology and positions, and cause oromandibular deformity. Common means for repairing alveolar bone defects include guided tissue regeneration, autologous bone grafting, artificial bone grafting, and the like. Where guided bone regeneration is difficult to provide adequate mechanical support to the larger alveolar bone defect site, autogenous bone grafting is a gold standard for alveolar bone regeneration, but has a problem of limited sources, in contrast to artificial bone grafting which has a wide material source and good biocompatibility. In order to achieve alveolar bone repair and regeneration, artificial bone grafting is further provided with: 1) Controllable degradation rate, degradation products are nontoxic; 2) Promoting cell proliferation and inducing osteoblast formation; 3) Mechanical strength similar to regenerated tissue. In addition, since patients have different degrees of defects and different shapes, the alveolar bone implant should be individually prepared to satisfy clinical applications.
At present, the artificial bone powder is mainly filled into the defect part for curing and forming clinically, so that the shaping is difficult, powder particles are easy to shift when the alveolar bone is filled in the early stage, and the powder particles are difficult to be attached to the anatomical form of the alveolar bone, so that the powder cannot be well fixed in the repairing process, and the alveolar bone is further absorbed. As 3D printing technology continues to develop, digital modeling in combination with laser selective fusion technology to personalize custom implants has become the best choice. The personalized customized implant is designed according to the defect part in situ, and then the powder is melted layer by utilizing the laser selective melting technology to form the alveolar bone implant which is closely attached to the anatomical shape, can be applied to horizontal bone defects, vertical bone defects and horizontal-vertical combined bone defects, and is particularly suitable for repairing the alveolar bone defects in a large area. Meanwhile, according to the personalized customized implant, the operation scheme can be formulated in advance, so that manual shaping in operation is avoided, and the operation time is greatly shortened. However, the accuracy of the shaping of a personalized custom implant is closely related to the powder flowability. For example, a powder with good flowability is advantageous for improving the powder spreading effect during printing, the shape accuracy of the implant is high, and the mechanical properties thereof are also relatively high. This difference is more pronounced, especially when the temperature is increased and the powder flowability is reduced. Therefore, how to prepare degradable alveolar bone implants which are tightly attached to different defect degrees and can induce repair and regeneration of defect parts becomes a difficult problem to be solved in clinic.
Disclosure of Invention
It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided a degradable hydroxyapatite/levorotatory polylactic acid alveolar bone implant made of a hydroxyapatite/levorotatory polylactic acid composite powder including 20 to 60% by mass of hydroxyapatite and 40 to 80% by mass of levorotatory polylactic acid through laser selective melt molding.
Preferably, the preparation method of the degradable hydroxyapatite/levorotatory polylactic acid alveolar bone implant comprises the following steps of: scanning the oral defect part of the patient by using a computer tomography technology to obtain tooth and jaw data, designing a three-dimensional structure model which is more fit with the anatomical form of the jaw of the patient by combining computer aided design software, and introducing the three-dimensional structure model into a laser selective fusion forming system; and placing the hydroxyapatite/levorotatory polylactic acid composite powder processed by ball milling, extrusion granulation, crushing into powder and spheroidizing process into laser selective melting, and printing layer by layer according to the modeled type to generate the personalized alveolar bone implant, wherein when the single layer is sintered, the laser scans twice, the first scanning is the X direction, and the second scanning is the Y direction.
Preferably, the laser scanning power is 0.8-1.3W, the scanning speed is 90-110 mm/s, and the printing thickness is 0.1-0.3 mm.
Preferably, the hydroxyapatite/levorotatory polylactic acid composite powder is prepared by mixing hydroxyapatite powder and levorotatory polylactic acid powder which are taken according to components through a ball mill, wherein the ball milling speed is 180-250 rpm, and the ball milling time is 1.5-2.5 hours.
Preferably, the hydroxyapatite/levorotatory polylactic acid composite powder after ball milling is formed and sheared into particles by an extruder, wherein the temperature of the feeding end of the extruder is 170-180 ℃, the temperature of the discharging end of the extruder is 180-190 ℃, and the rotating speed of the extruder is 95-115 rpm.
Preferably, the sheared particles are crushed into powder with the particle size smaller than 70 mu m by a liquid nitrogen crusher, the precooling temperature of the liquid nitrogen crusher is 150-180 ℃, the crushing temperature is 150-180 ℃, the rotating speed of a main machine is 45-47 rpm, the rotating speed of a fan is 8-12 rpm, and the rotating speed of a discharge hole is 5-7 rpm.
Preferably, the crushed hydroxyapatite/levorotatory polylactic acid composite powder is sphericized by an air fluidized bed device, the repose angle after sphericization is less than or equal to 34 degrees, the heating temperature of the air fluidized bed device is 220-240 ℃, and the feeding rotating speed is 5-7 rpm per minute.
Preferably, before ball-milling and mixing the hydroxyapatite powder and the levorotatory polylactic acid powder, the hydroxyapatite powder is subjected to enhancement treatment by using polyether ketone, and the enhancement treatment method comprises the following steps: weighing 15-20 parts by weight of polyether-ketone powder, heating and melting the polyether-ketone powder into a liquid state, mixing 30-50 parts by weight of hydroxyapatite powder with the liquid polyether-ketone, uniformly stirring, cooling to room temperature, crushing, adopting wet grinding, selecting sucrose ester as a dispersing agent, using 45-80 parts by weight of deionized water as a grinding medium, wherein the corundum ball accounting for 5% of the total mass of the deionized water, the polyether-ketone and the hydroxyapatite is 0.4% of the dispersing agent, the grinding speed is 1500-1800 r/min, the grinding time is 3-12 h, and separating to obtain the polyether-ketone-enhanced hydroxyapatite powder.
Preferably, before the hydroxyapatite powder and the levorotatory polylactic acid powder are subjected to ball milling and mixing, the surface of the levorotatory polylactic acid powder is modified by using polydopamine and triethylamine, and the modification method comprises the following steps: weighing 500mg of dopamine, dissolving in 300mL of Tris-HCl buffer solution, wherein the pH value of the Tris-HCl buffer solution is 8-9, preparing a polydopamine solution, weighing 0.8mg of levorotatory polylactic acid powder, putting the polydopamine solution, and uniformly preparing polydopamine modified levorotatory polylactic acid suspension through first magnetic stirring and first ultrasonic dispersion and mixing; adding 20mg of triethylamine into the left-handed polylactic acid suspension, and performing magnetic stirring and ultrasonic dispersion for the second time to obtain a mixed suspension; wherein, the first magnetic stirring rotating speed is 600-800 r/min, the first ultrasonic dispersing time is 50min, the first ultrasonic dispersing frequency is 25-40 kHz, the second magnetic stirring rotating speed is 400-600 r/min, the second ultrasonic dispersing time is 30min, and the second ultrasonic dispersing frequency is 30-50 kHz;
carrying out centrifugal separation on the prepared mixed suspension, washing with distilled water, drying and grinding to prepare the surface-modified levorotatory polylactic acid of polydopamine and triethylamine; wherein the rotational speed of centrifugal separation is 1600-1800 r/min, the centrifugal separation time is 20-30 min, and the drying temperature is 50-55 ℃.
The invention at least comprises the following beneficial effects: the L-polylactic acid has excellent biocompatibility, and is degraded by water or enzyme, so that the product is nontoxic. However, the mechanical strength is poor and the degradation products are acidic, which easily causes an inflammatory reaction to occur, resulting in further resorption of the defective alveolar bone. Hydroxyapatite has high biocompatibility and excellent osteogenic activity similar to human tissue components. The mechanical strength of the modified polylactic acid can be effectively improved by introducing the modified polylactic acid into the levorotatory polylactic acid as an inorganic phase. Since the degradation products of the hydroxyapatite are alkaline, the acidic products of the levorotatory polylactic acid can be neutralized. Meanwhile, the free calcium and phosphorus are released by degradation, and can be absorbed and utilized by human tissues, so that new tissues are formed, and the bone conduction effect is exerted. More importantly, the hydroxyapatite is combined with human cell membrane surface layer polysaccharide and protein through hydrogen bonds, so that the combination between surrounding normal tissues and the implant can be promoted.
The hydroxyapatite powder and the L-polylactic acid powder are mixed, the particle form is irregular, the repose angle is more than or equal to 40 degrees, and poor fluidity is shown. Powder chapping is easy to cause in the laser printing process, and the powder spreading effect is reduced. This causes the printed implant to show more defects, degrading its performance; on the other hand, the printed implant has low molding accuracy, and it is difficult to form a tight fit with the defective alveolar bone, thereby eventually leading to failure of the alveolar bone graft.
Compared with the prior art, the invention has the advantages that:
(1) The hydroxyapatite/levorotatory polylactic acid composite alveolar bone implant adopted by the invention can be naturally degraded and release calcium and phosphorus in a free state, can be absorbed and utilized by surrounding tissues, promotes proliferation and growth of cells, simultaneously induces bone cell formation, and overcomes the difficult problem that alveolar bone is difficult to regenerate due to insufficient bone mass.
(2) The alveolar bone implant adopted by the invention is made of polymer-based materials, the weight and the compression strength of the implant are closer to those of human bones, the implant can not bring uncomfortable feeling to patients, and the implant has good heat insulation, can adapt to cold and hot environments in oral cavities, and has good safety and effectiveness when being implanted into the oral cavities.
(3) The invention obtains the hydroxyapatite/levorotatory polylactic acid composite powder which is uniformly mixed, regular in shape and good in fluidity through the ball milling, extrusion granulation, powder grinding and spheroidizing process, which is beneficial to powder spreading in the printing process and avoids various defects and reduction of forming precision in the sintering process.
(4) According to the defect part of the alveolar bone, the alveolar bone implant is prepared in a personalized way by utilizing a laser selective melting technology, can be tightly attached to the anatomical shape of the alveolar bone, and is not easy to fall off in the use process.
(5) The invention uses the polyether ketone to carry out enhancement treatment on the hydroxyapatite powder, uses the polydopamine and the triethylamine to carry out surface modification on the levorotatory polylactic acid powder, further improves the mechanical strength of the hydroxyapatite/levorotatory polylactic acid composite powder obtained after mixing, and ensures that the prepared degradable hydroxyapatite/levorotatory polylactic acid alveolar bone implant has better mechanical property and ultimate compressive strength.
In conclusion, the invention solves the difficult problems of difficult repair and regeneration of the defective alveolar bone due to insufficient bone quantity and different defective forms. The hydroxyapatite/levorotatory polylactic acid composite implant can be naturally degraded, and degradation products can be absorbed and utilized by surrounding tissues, so that proliferation of cells and formation of bone cells are promoted. The alveolar bone implant has mechanical strength similar to that of regenerated tissue, and can provide effective supporting effect for chewing of the mouth. The invention obtains composite powder with uniform mixing, regular shape and good fluidity through the ball milling, extrusion granulation, powder grinding and spheroidizing process, and then precisely prints out the alveolar bone implant by utilizing the laser selective melting technology according to the defect part of the alveolar bone, thereby having high forming precision, being capable of being tightly attached to the anatomical shape of the alveolar bone, being not easy to fall off in the use process and finally achieving the effects of repairing and regenerating the defect alveolar bone.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a morphology diagram of stem cells after 7 days of culture in the degradable hydroxyapatite/L-polylactic acid alveolar bone implant extract prepared by the invention;
FIG. 2 is a graph showing the detection of alkaline phosphatase staining of stem cells after 10 days of culture of the degradable hydroxyapatite/L-polylactic acid alveolar bone implant extract prepared by the present invention.
Detailed Description
The present invention is described in further detail below with reference to the drawings to enable those skilled in the art to practice the invention by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1
Weighing and preparing mixed powder of 20% of hydroxyapatite and 80% of L-polylactic acid by using an electronic balance; the powder is prepared into composite powder with regular shape and good fluidity through a ball milling, extrusion granulation, crushing into powder, spheroidizing and balling process, and then the composite powder is placed into a laser selective melting system; wherein, the ball milling rotating speed is 180rpm, and the ball milling time is 2.5 hours; extruding and granulating the ball-milled composite powder, shearing the powder into particles, wherein the temperature of a feeding end of an extruder is 170 ℃, the temperature of a discharging end of the extruder is 180 ℃, and the rotating speed of the extruder is 95rpm; the sheared particles are crushed into powder with the particle size smaller than 70 mu m by a liquid nitrogen crusher, the precooling temperature of the liquid nitrogen crusher is 150 ℃, the crushing temperature is 150 ℃, the rotating speed of a main machine is 45rpm, the rotating speed of a fan is 8rpm, and the rotating speed of a discharge hole is 5rpm; placing the crushed irregular powder into a vacuum drying oven, and drying for 12 hours in a vacuum atmosphere at the temperature of 60 ℃; the dried hydroxyapatite/levorotatory polylactic acid composite powder is subjected to sphericizing by air fluidized bed equipment, the repose angle after sphericizing is less than or equal to 34 degrees, the heating temperature of the air fluidized bed equipment is 220 ℃, and the feeding rotating speed is 5rpm per minute; scanning the oral defect part of a patient by using a computer tomography technology, importing the acquired data into three-dimensional modeling software to reconstruct a three-dimensional model of the oral defect part, establishing a three-dimensional structure model closely fitting the anatomical form of the alveolar bone, importing the generated STL file into a laser selective melting system, and finally printing out a personalized degradable implant matched with the alveolar bone by using high energy of laser; when the scanning strategy is single-layer sintering, the laser is scanned twice, the first scanning is X-direction scanning, the second scanning is Y-direction scanning, the laser power is 1W, the scanning speed is 100mm/s, and the thickness of the printing layer is 0.2mm.
Through the discovery of a scanning electron microscope, the hydroxyapatite/levorotatory polylactic acid composite powder with regular shape is prepared through the ball milling-extrusion granulation-powder grinding-spheroidizing process, and the repose angle is 31.2 degrees, so that the composite powder shows good fluidity.
The degradable alveolar bone implant printed using the composite powder having good fluidity was observed, and the result showed no significant defect and high shape accuracy.
The mechanical property test shows that the ultimate compressive strength of the degradable hydroxyapatite/levorotatory polylactic acid composite implant is 40MPa, which is similar to the mechanical strength of regenerated tissues.
The biocompatibility test shows that the degradable hydroxyapatite/levorotatory polylactic acid composite implant can promote cell proliferation and induce bone cell generation as shown in fig. 1 and 2.
Example 2
Weighing and preparing mixed powder of 35% of hydroxyapatite and 65% of L-polylactic acid by using an electronic balance; the powder is prepared into hydroxyapatite/L-polylactic acid composite powder with regular shape and good fluidity by ball milling, extrusion granulation, crushing into powder, spheroidizing and balling process, and then the composite powder is placed into a laser selective melting system; wherein, the ball milling rotating speed is 200rpm, and the ball milling time is 2 hours; extruding and granulating the ball-milled composite powder, shearing the powder into particles, wherein the temperature of a feeding end of an extruder is 175 ℃, the temperature of a discharging end of the extruder is 185 ℃, and the rotating speed of the extruder is 95rpm; the sheared particles are crushed into powder with the particle size smaller than 70 mu m by a liquid nitrogen crusher, the precooling temperature of the liquid nitrogen crusher is 160 ℃, the crushing temperature is 160 ℃, the rotating speed of a main machine is 46rpm, the rotating speed of a fan is 10rpm, and the rotating speed of a discharge hole is 6rpm; placing the crushed irregular powder into a vacuum drying oven, and drying for 12 hours in a vacuum atmosphere at the temperature of 60 ℃; the dried hydroxyapatite/levorotatory polylactic acid composite powder is subjected to sphericizing by air fluidized bed equipment, the repose angle after sphericizing is less than or equal to 34 degrees, the heating temperature of the air fluidized bed equipment is 230 ℃, and the feeding speed is 6rpm per minute; scanning the oral defect part of a patient by using a computer tomography technology, importing the acquired data into three-dimensional modeling software to reconstruct a three-dimensional model of the oral defect part, establishing a three-dimensional structure model closely fitting the anatomical form of the alveolar bone, importing the generated STL file into a laser selective melting system, and finally printing out a personalized degradable implant matched with the alveolar bone by using high energy of laser; when the scanning strategy is single-layer sintering, the laser is scanned twice, the first scanning is X-direction scanning, the second scanning is Y-direction scanning, the laser power is 1W, the scanning speed is 100mm/s, and the thickness of the printing layer is 0.2mm.
The scanning electron microscope shows that the hydroxyapatite/levorotatory polylactic acid composite powder with regular shape is prepared by the ball milling-extrusion granulation-powder grinding-spheroidizing process, the repose angle is 32.4 degrees, and the good fluidity is shown.
The degradable alveolar bone implant printed using the composite powder having good fluidity was observed, and the result showed no significant defect and high shape accuracy.
The mechanical property test shows that the ultimate compressive strength of the degradable hydroxyapatite/levorotatory polylactic acid composite implant is 31MPa, which is similar to the mechanical strength of regenerated tissues.
The biocompatibility test shows that the degradable hydroxyapatite/levorotatory polylactic acid composite implant can promote cell proliferation and induce bone cell generation.
Example 3
Weighing and preparing mixed powder of 60% of hydroxyapatite and 40% of levorotatory polylactic acid by using an electronic balance; the powder is prepared into hydroxyapatite/L-polylactic acid composite powder with regular shape and good fluidity by ball milling, extrusion granulation, crushing into powder, spheroidizing and balling process, and then the composite powder is placed into a laser selective melting system; wherein, the ball milling rotating speed is 250rpm, and the ball milling time is 1.5 hours; extruding and granulating the ball-milled composite powder, shearing the powder into particles, wherein the temperature of the feeding end of an extruder is 180 ℃, the temperature of the discharging end of the extruder is 190 ℃, and the rotating speed of the extruder is 115rpm; the sheared particles are crushed into powder with the particle size smaller than 70 mu m by a liquid nitrogen crusher, the precooling temperature of the liquid nitrogen crusher is 150 ℃, the crushing temperature is 150 ℃, the rotating speed of a main machine is 46rpm, the rotating speed of a fan is 9rpm, and the rotating speed of a discharge hole is 6rpm; placing the crushed irregular powder into a vacuum drying oven, and drying for 12 hours in a vacuum atmosphere at the temperature of 60 ℃; the dried hydroxyapatite/levorotatory polylactic acid composite powder is subjected to sphericizing by air fluidized bed equipment, the repose angle after sphericizing is less than or equal to 34 degrees, the heating temperature of the air fluidized bed equipment is 240 ℃, and the feeding rotating speed is 7rpm per minute; scanning the oral defect part of a patient by using a computer tomography technology, importing the acquired data into three-dimensional modeling software to reconstruct a three-dimensional model of the oral defect part, establishing a three-dimensional structure model closely fitting the anatomical form of the alveolar bone, importing the generated STL file into a laser selective melting system, and finally printing out a personalized degradable implant matched with the alveolar bone by using high energy of laser; when the scanning strategy is single-layer sintering, the laser is scanned twice, the first scanning is X-direction scanning, the second scanning is Y-direction scanning, the laser power is 1W, the scanning speed is 100mm/s, and the thickness of the printing layer is 0.2mm.
Through the discovery of a scanning electron microscope, the hydroxyapatite/levorotatory polylactic acid composite powder with regular shape is prepared through the ball milling-extrusion granulation-powder grinding-spheroidizing process, and the repose angle is 33.5 degrees, so that the composite powder shows good fluidity.
The degradable alveolar bone implant printed using the composite powder having good fluidity was observed, and the result showed no significant defect and high shape accuracy.
The mechanical property test shows that the ultimate compressive strength of the degradable hydroxyapatite/levorotatory polylactic acid composite implant is 20MPa, which is similar to the mechanical strength of regenerated tissues.
The biocompatibility test shows that the degradable hydroxyapatite/levorotatory polylactic acid composite implant can promote cell proliferation and induce bone cell generation.
Example 4
Weighing and preparing mixed powder of 60% of hydroxyapatite and 40% of levorotatory polylactic acid by using an electronic balance; before ball milling and mixing the hydroxyapatite powder and the levorotatory polylactic acid powder, the hydroxyapatite powder is subjected to enhancement treatment by using polyether ketone, and the enhancement treatment method comprises the following steps: weighing 1500mg of polyether-ketone powder according to parts by weight, heating and melting the polyether-ketone powder into a liquid state, mixing and stirring hydroxy 3000mg of hydroxyapatite powder and liquid polyether-ketone uniformly, cooling to room temperature, crushing, adopting wet grinding, selecting sucrose ester as a dispersing agent, using 450mg of corundum sphere as a grinding medium, wherein the dosage of the dispersing agent is 36mg, the grinding speed is 1500r/min, the grinding time is 3h, and separating to obtain the polyether-ketone-enhanced hydroxyapatite powder.
The method for carrying out surface modification on the L-polylactic acid powder by using polydopamine and triethylamine comprises the following steps: weighing 500mg of dopamine, dissolving in 300mL of Tris-HCl buffer solution, preparing a polydopamine solution, weighing 0.8mg of L-polylactic acid powder, putting the polydopamine solution, and uniformly preparing a polydopamine modified L-polylactic acid suspension by first magnetic stirring and first ultrasonic dispersion and mixing; adding 20mg of triethylamine into the left-handed polylactic acid suspension, and performing magnetic stirring and ultrasonic dispersion for the second time to obtain a mixed suspension; wherein, the first magnetic stirring rotating speed is 600r/min, the first ultrasonic dispersing time is 50min, the first ultrasonic dispersing frequency is 25kHz, the second magnetic stirring rotating speed is 400r/min, the second ultrasonic dispersing time is 30min, and the second ultrasonic dispersing frequency is 30kHz;
carrying out centrifugal separation on the prepared mixed suspension, washing with distilled water, drying and grinding to prepare the surface-modified levorotatory polylactic acid of polydopamine and triethylamine; wherein the rotation speed of centrifugal separation is 1600r/min, the centrifugal separation time is 20min, and the drying temperature is 50 ℃;
preparing hydroxyapatite/levorotatory polylactic acid composite powder with regular shape and good fluidity by ball milling, extrusion granulation, crushing and spheroidizing process of the surface-modified levorotatory polylactic acid powder of the hydroxyapatite powder, the polydopamine and the triethylamine reinforced by the polyetherketoneketone, and then placing the composite powder into a laser selective melting system; wherein, the ball milling rotating speed is 250rpm, and the ball milling time is 1.5 hours; extruding and granulating the ball-milled composite powder, shearing the powder into particles, wherein the temperature of the feeding end of an extruder is 180 ℃, the temperature of the discharging end of the extruder is 190 ℃, and the rotating speed of the extruder is 115rpm; the sheared particles are crushed into powder with the particle size smaller than 70 mu m by a liquid nitrogen crusher, the precooling temperature of the liquid nitrogen crusher is 150 ℃, the crushing temperature is 150 ℃, the rotating speed of a main machine is 46rpm, the rotating speed of a fan is 9rpm, and the rotating speed of a discharge hole is 6rpm; placing the crushed irregular powder into a vacuum drying oven, and drying for 12 hours in a vacuum atmosphere at the temperature of 60 ℃; the dried hydroxyapatite/levorotatory polylactic acid composite powder is subjected to sphericizing by air fluidized bed equipment, the repose angle after sphericizing is less than or equal to 34 degrees, the heating temperature of the air fluidized bed equipment is 240 ℃, and the feeding rotating speed is 7rpm per minute; scanning the oral defect part of a patient by using a computer tomography technology, importing the acquired data into three-dimensional modeling software to reconstruct a three-dimensional model of the oral defect part, establishing a three-dimensional structure model closely fitting the anatomical form of the alveolar bone, importing the generated STL file into a laser selective melting system, and finally printing out a personalized degradable implant matched with the alveolar bone by using high energy of laser; when the scanning strategy is single-layer sintering, the laser is scanned twice, the first scanning is X-direction scanning, the second scanning is Y-direction scanning, the laser power is 1W, the scanning speed is 100mm/s, and the thickness of the printing layer is 0.2mm.
The degradable alveolar bone implant printed using the composite powder having good fluidity was observed, and the result showed no significant defect and high shape accuracy.
The mechanical property test shows that the ultimate compressive strength of the degradable hydroxyapatite/levorotatory polylactic acid composite implant is 44.5MPa, which is similar to the mechanical strength of regenerated tissues.
The biocompatibility test shows that the degradable hydroxyapatite/levorotatory polylactic acid composite implant can promote cell proliferation and induce bone cell generation.
Example 5
Weighing and preparing mixed powder of 60% of hydroxyapatite and 40% of levorotatory polylactic acid by using an electronic balance; before ball milling and mixing the hydroxyapatite powder and the levorotatory polylactic acid powder, the hydroxyapatite powder is subjected to enhancement treatment by using polyether ketone, and the enhancement treatment method comprises the following steps: weighing 2000mg of polyether ketone powder according to parts by weight, heating and melting the polyether ketone powder into liquid, uniformly mixing and stirring 5000mg of hydroxy apatite powder and liquid polyether ketone, cooling to room temperature, crushing, adopting wet grinding, sucrose ester is selected as a dispersing agent, and the deionized water is taken as a grinding medium, wherein the dosage of the dispersing agent is 60mg, the grinding speed is 1800r/min, the grinding time is 6h, and the polyether ketone enhanced hydroxyapatite powder is obtained by separation.
The method for carrying out surface modification on the L-polylactic acid powder by using polydopamine and triethylamine comprises the following steps: weighing 500mg of dopamine, dissolving in 300mL of Tris-HCl buffer solution, wherein the pH value of the Tris-HCl buffer solution is 9, preparing a polydopamine solution, weighing 0.8mg of L-polylactic acid powder, putting the polydopamine solution, and uniformly preparing a polydopamine modified L-polylactic acid suspension through first magnetic stirring and first ultrasonic dispersion and mixing; adding 20mg of triethylamine into the left-handed polylactic acid suspension, and performing magnetic stirring and ultrasonic dispersion for the second time to obtain a mixed suspension; wherein, the first magnetic stirring rotating speed is 800r/min, the first ultrasonic dispersing time is 50min, the first ultrasonic dispersing frequency is 40kHz, the second magnetic stirring rotating speed is 600r/min, the second ultrasonic dispersing time is 30min, and the second ultrasonic dispersing frequency is 50kHz;
carrying out centrifugal separation on the prepared mixed suspension, washing with distilled water, drying and grinding to prepare the surface-modified levorotatory polylactic acid of polydopamine and triethylamine; wherein the rotation speed of centrifugal separation is 1800r/min, the centrifugal separation time is 30min, and the drying temperature is 55 ℃;
preparing hydroxyapatite/levorotatory polylactic acid composite powder with regular shape and good fluidity by ball milling, extrusion granulation, crushing and spheroidizing process of the surface-modified levorotatory polylactic acid powder of the hydroxyapatite powder, the polydopamine and the triethylamine reinforced by the polyetherketoneketone, and then placing the composite powder into a laser selective melting system; wherein, the ball milling rotating speed is 250rpm, and the ball milling time is 1.5 hours; extruding and granulating the ball-milled composite powder, shearing the powder into particles, wherein the temperature of the feeding end of an extruder is 180 ℃, the temperature of the discharging end of the extruder is 190 ℃, and the rotating speed of the extruder is 115rpm; the sheared particles are crushed into powder with the particle size smaller than 70 mu m by a liquid nitrogen crusher, the precooling temperature of the liquid nitrogen crusher is 150 ℃, the crushing temperature is 150 ℃, the rotating speed of a main machine is 46rpm, the rotating speed of a fan is 9rpm, and the rotating speed of a discharge hole is 6rpm; placing the crushed irregular powder into a vacuum drying oven, and drying for 12 hours in a vacuum atmosphere at the temperature of 60 ℃; the dried hydroxyapatite/levorotatory polylactic acid composite powder is subjected to sphericizing by air fluidized bed equipment, the repose angle after sphericizing is less than or equal to 34 degrees, the heating temperature of the air fluidized bed equipment is 240 ℃, and the feeding rotating speed is 7rpm per minute; scanning the oral defect part of a patient by using a computer tomography technology, importing the acquired data into three-dimensional modeling software to reconstruct a three-dimensional model of the oral defect part, establishing a three-dimensional structure model closely fitting the anatomical form of the alveolar bone, importing the generated STL file into a laser selective melting system, and finally printing out a personalized degradable implant matched with the alveolar bone by using high energy of laser; when the scanning strategy is single-layer sintering, the laser is scanned twice, the first scanning is X-direction scanning, the second scanning is Y-direction scanning, the laser power is 1W, the scanning speed is 100mm/s, and the thickness of the printing layer is 0.2mm.
The degradable alveolar bone implant printed using the composite powder having good fluidity was observed, and the result showed no significant defect and high shape accuracy.
The mechanical property test shows that the ultimate compressive strength of the degradable hydroxyapatite/levorotatory polylactic acid composite implant is 45.2MPa, which is similar to the mechanical strength of regenerated tissues.
The biocompatibility test shows that the degradable hydroxyapatite/levorotatory polylactic acid composite implant can promote cell proliferation and induce bone cell generation.
Comparative example 1
Other conditions were the same as in example 1, except that: weighing mixed powder of 20% of hydroxyapatite and 80% of L-polylactic acid by using an electronic balance, and directly placing the mixed powder into a laser selective melting system; the scanning electron microscope shows that the hydroxyapatite/levorotatory polylactic acid composite powder has irregular shape, poor fluidity, an repose angle of 40.7 degrees, obvious defects of the personalized prepared alveolar bone implant, low forming precision and ultimate compressive strength of 17MPa.
The number of equipment and the scale of processing described herein are intended to simplify the description of the present invention. Applications, modifications and variations of the present invention will be readily apparent to those skilled in the art.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention would be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (7)
1. The preparation method of the degradable hydroxyapatite/left-handed polylactic acid alveolar bone implant is characterized in that the degradable hydroxyapatite/left-handed polylactic acid alveolar bone implant is prepared by performing laser selective fusion forming on hydroxyapatite/left-handed polylactic acid composite powder, wherein the hydroxyapatite/left-handed polylactic acid composite powder comprises 20-60% of hydroxyapatite by mass and 40-80% of left-handed polylactic acid by mass;
the preparation method of the degradable hydroxyapatite/levorotatory polylactic acid alveolar bone implant comprises the following steps: scanning the oral defect part of the patient by using a computer tomography technology to obtain tooth and jaw data, designing a three-dimensional structure model which is more fit with the anatomical form of the jaw of the patient by combining computer aided design software, and introducing the three-dimensional structure model into a laser selective fusion forming system; placing the hydroxyapatite/levorotatory polylactic acid composite powder processed by ball milling, extrusion granulation, crushing into powder and spheroidization process into a laser selected area for melting, and printing layer by layer according to a modeled type to generate the personalized alveolar bone implant, wherein when the single layer is sintered, the laser scans twice, the first scanning is in the X direction, and the second scanning is in the Y direction;
before ball milling and mixing the hydroxyapatite powder and the levorotatory polylactic acid powder, the hydroxyapatite powder is subjected to enhancement treatment by using polyether ketone, and the enhancement treatment method comprises the following steps: weighing 15-20 parts by weight of polyether-ketone powder, heating and melting the polyether-ketone powder into a liquid state, uniformly mixing 30-50 parts by weight of hydroxyapatite powder with the liquid polyether-ketone, cooling to room temperature, crushing, adopting wet grinding, selecting sucrose ester as a dispersing agent, and using 45-80 parts by weight of deionized water as a grinding medium, wherein the corundum ball accounting for 5% of the total mass of the deionized water, the polyether-ketone and the hydroxyapatite, the dispersing agent accounts for 0.4% of the total mass of the deionized water, the polyether-ketone and the hydroxyapatite, the grinding speed is 1500-1800 r/min, the grinding time is 3-12 h, and separating to obtain the polyether-ketone-enhanced hydroxyapatite powder;
before carrying out ball milling mixing on hydroxyapatite powder and levorotatory polylactic acid powder, carrying out surface modification on the levorotatory polylactic acid powder by using polydopamine and triethylamine, wherein the modification method comprises the following steps: weighing 500mg of dopamine, dissolving in 300mL of Tris-HCl buffer solution, wherein the pH value of the Tris-HCl buffer solution is 8-9, preparing a polydopamine solution, weighing 0.8mg of levorotatory polylactic acid powder, putting the polydopamine solution, and uniformly preparing polydopamine modified levorotatory polylactic acid suspension through first magnetic stirring and first ultrasonic dispersion and mixing; adding 20mg of triethylamine into the left-handed polylactic acid suspension, and performing magnetic stirring and ultrasonic dispersion for the second time to obtain a mixed suspension; the first magnetic stirring speed is 600-800 r/min, the first ultrasonic dispersing time is 50min, the first ultrasonic dispersing frequency is 25-40 kHz, the second magnetic stirring speed is 400-600 r/min, the second ultrasonic dispersing time is 30min, and the second ultrasonic dispersing frequency is 30-50 kHz;
carrying out centrifugal separation on the prepared mixed suspension, washing with distilled water, drying and grinding to prepare the surface-modified levorotatory polylactic acid of polydopamine and triethylamine; the rotational speed of centrifugal separation is 1600-1800r/min, the centrifugal separation time is 20-30 min, and the drying temperature is 50-55 ℃.
2. The method for preparing the degradable hydroxyapatite/levorotatory polylactic acid alveolar bone implant according to claim 1, wherein the laser scanning power is 0.8-1.3 w, the scanning speed is 90-110 mm/s, and the printing thickness is 0.1-0.3 mm.
3. The method for preparing the degradable hydroxyapatite/levorotatory polylactic acid alveolar bone implant according to claim 1, wherein the hydroxyapatite/levorotatory polylactic acid composite powder is prepared by mixing hydroxyapatite powder and levorotatory polylactic acid powder which are taken according to components through a ball mill, wherein the ball milling speed is 180-250 rpm, and the ball milling time is 1.5-2.5 hours.
4. The method for preparing the degradable hydroxyapatite/levorotatory polylactic acid alveolar bone implant according to claim 1, wherein the hydroxyapatite/levorotatory polylactic acid composite powder after ball milling is formed and sheared into particles through an extruder, the temperature of the feeding end of the extruder is 170-180 ℃, the temperature of the discharging end of the extruder is 180-190 ℃, and the rotating speed of the extruder is 95-115 rpm.
5. The method for preparing a degradable hydroxyapatite/levorotatory polylactic acid alveolar bone implant according to claim 4 wherein the sheared particles are crushed into powder having a particle size of less than 70 μm using a liquid nitrogen crusher.
6. The method for preparing a degradable hydroxyapatite/levorotatory polylactic acid alveolar bone implant according to claim 1, wherein the crushed hydroxyapatite/levorotatory polylactic acid composite powder is placed in a vacuum box and dried for 12 hours under a vacuum atmosphere at a drying temperature of 60 ℃.
7. The method for preparing the degradable hydroxyapatite/levorotatory polylactic acid alveolar bone implant according to claim 1, wherein the crushed hydroxyapatite/levorotatory polylactic acid composite powder is sphericized by an air fluidized bed device, the repose angle after sphericization is less than or equal to 34 degrees, the heating temperature of the air fluidized bed device is 220-240 ℃, and the feeding speed is 5-7 rpm.
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| EP3412682A1 (en) * | 2013-03-15 | 2018-12-12 | Trustees Of Tufts College | Low molecular weight silk compositions and stabilizing silk compositions |
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| CN107823712A (en) * | 2017-12-13 | 2018-03-23 | 华中科技大学 | A kind of method for preparing imitative artificial bone of coral with cuttlebone and products thereof |
| CN111184916A (en) * | 2018-11-15 | 2020-05-22 | 中南大学 | Method for preparing hydroxyapatite/levorotatory polylactic acid composite bone scaffold |
| CN109568669A (en) * | 2018-11-30 | 2019-04-05 | 重庆医科大学附属永川医院 | A kind of implantation material and preparation method thereof fixed for backbone reparation |
| CN114470318A (en) * | 2022-01-26 | 2022-05-13 | 江苏迈伦医疗科技有限公司 | Method for preparing porous bioceramic artificial bone based on selective laser sintering |
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