CN115054738B

CN115054738B - Degradable zinc alloy nasal sinus support

Info

Publication number: CN115054738B
Application number: CN202210989587.8A
Authority: CN
Inventors: 张海军; 周广泰; 初同超; 周超
Original assignee: Shandong Rientech Medical Technology Co ltd
Current assignee: Shandong Rientech Medical Technology Co ltd
Priority date: 2022-08-18
Filing date: 2022-08-18
Publication date: 2022-10-28
Anticipated expiration: 2042-08-18
Also published as: CN115054738A

Abstract

The invention belongs to the field of medical appliances, and discloses a degradable zinc alloy sinus stent which is prepared by vacuum melting. The zinc-based alloy has good mechanical property, is easy to process, and has the properties of strength, toughness, plasticity and the like which meet the requirements of human implant materials such as nasal meatus and the like; the surface of the bracket is coated with therapeutic drugs; the four elements of Zn, fe, mg and Cu are all necessary elements for human bodies, and zinc ions can enhance the immunity of the human bodies and also help the healing of wounds and wounds; magnesium is an activator and a cofactor of various enzymes, and can catalyze the activation of the enzymes and inhibit the cell cycle, the cell proliferation and the cell differentiation; iron can improve immunity, increase phagocytic function of neutrophil and phagocyte, and enhance anti-infection ability; the degradation product of copper has certain antibacterial effect; the zinc alloy stent has good biological performance, and the degradation process and the product are safe and effective to the body.

Description

Degradable zinc alloy nasal sinus support

Technical Field

The invention belongs to the field of medical instruments, and relates to a degradable zinc alloy sinus stent.

Background

The chronic nasosinusitis (CRS) takes nasal obstruction, sticky nasal discharge or purulent nasal discharge as main symptoms, and takes distending pain, hyposmia or disappearance, sleep disorder and fatigue of the head and face as secondary symptoms, and the treatment measures comprise drug treatment and operation treatment; first line treatments are saline nasal irrigation and intranasal corticosteroid spray; the main problem with CRS is inflammation caused by sinus ostial occlusion of the nasal tract, drug therapy is aimed at inhibiting this inflammatory state, corticosteroids are an integral part of the medical management of this disease; functional Endoscopic Sinus Surgery (FESS) is an important medical treatment aid for CRS, aiming to create a patent sinus ostium to effectively provide local treatment; the success rate of total CRS cure is as high as 98% by the development of surgical technology and the progress of instruments and the treatment of intensified medicines; in addition, the nasal sinuses and the nasal mucosa are easy to be adhered within the latter half month of the operation, and the adhesion can block the normal ventilation function, so that the symptom is not obviously improved or even ineffective, and further medication and (or) secondary operation are needed.

The common reasons for failure of the operation are repeated inflammation and polyp recurrence, scar formation adhesion, medial turbinate localization leading to narrow adhesion of the middle nasal passage and blockage of the enlarged sinus ostia of the operation, so how to effectively treat the nasosinusitis and control the complications and recurrence rate is particularly important.

The Propel bioabsorbable drug-eluting sinus stent developed by interject ENT company is approved by the Food and Drug Administration (FDA) in 2011, is made of biodegradable polymers, is implanted in an ethmoid sinus cavity after operation, can realize drug slow release, and has 35% of patients without secondary operation intervention; a series of stent products for treating chronic nasosinusitis, such as Propel Container and Sinuva, are developed in succession by the Intersect ENT, the Propel Container sinus stent has stronger plasticity and is more easily attached to the sinus, the Sinuva stent can reduce nasal polyp and relieve symptoms such as nasal obstruction after being implanted, and the sinus stent can be automatically degraded one month after being implanted.

5363A totally degradable sinus drug stent system developed by Pu Yi (Shanghai) Biotechnology Limited is used as the first example of degradable drug sinus stent in China, and is formally approved by the food and drug administration (CFDA) in 2017; the stent is made of a high-molecular degradable polymeric material, so that one-month degradation after operation can be realized, and a patient does not need to take out the stent after the operation; the surface of the stent is attached with a drug coating, and the drug can be slowly released at a lesion part along with the stent, so that adhesion, sinus ostial occlusion and the like after FESS operation can be effectively prevented.

In clinical contrast tests in which degradable and non-degradable medical grade materials are implanted respectively after FESS surgery, the therapeutic effect of the degradable material is found to have certain comprehensive advantages compared with that of the non-degradable material. At present, the trend of using the drug-eluting degradable stent in the nasal sinus surgery is more and more obvious, and the drug-coated stent is beneficial to helping the drug to reach the pathological change part so as to reduce inflammation, infection and the like.

CN 109758278A provides a self-expandable sinus stent and a taking and placing device thereof, so that the medicine can accurately and directly reach the diseased region of a patient, the medicine treatment effect is improved, and the treatment period is shortened.

CN 109106483A is a sinus stent which can completely degrade high molecular materials, can accurately deliver drugs to pathological parts in nasal cavities, can achieve the purpose of complete degradation, and is safe and reliable for nasal cavities; the advantages are that (1) has good drug release capacity, minimal acute recoil action and excellent adaptability; (2) The transition from the stent to the discontinuous structure, gradually losing radial support force, the stent becomes discontinuous in structure; (3) The implant is structurally discontinuous, broken, has lost performance, is absorbed in a benign manner, and dissolves by itself, leaving no traces, two years later. The disadvantages are that: (1) The hardness increases the operation difficulty, and accidents may occur; (2) relatively brittle and sometimes subject to in vivo fracture; (3) The high molecular material has low mechanical strength, and degradation products cause local aseptic inflammation.

CN106137482a discloses a sinus stent extending along a longitudinal axis and loaded with a drug, comprising: the supporting rod is of a straight tubular structure and is provided with a top end and a free end, and a clamping structure protruding outwards in the radial direction is arranged on the pipe wall of the supporting rod close to the free end; and the cover is located the sleeve pipe on this bracing piece outer wall, and this sleeve pipe has annular link and expansion end, is provided with many connecting spokes that separate the setting each other between this link and expansion end, the top with link fixed connection, the expansion end can block in block the structure, but this sinus support is comparatively complicated, and the preparation process is loaded down with trivial details.

CN 107898540A provides a combination of a nasal sinus sacculus catheter and a sacculus expansion type nasal stent, which is used for treating nasal-nasal sinusitis, the sacculus expansion type nasal stent is implanted into a diseased nasal sinus or nasal cavity after an operation, and the nasal sinus or nasal cavity is supported, so that inflammation of the nasal sinus or nasal cavity is eliminated, and mucosa of the nasal sinus or nasal cavity is prevented from being adhered.

The patent CN 106890356A discloses a degradable zinc-based alloy implant material, a preparation method and application thereof, and the alloy elongation is 12 to 24 percent.

The patent application CN 109939271A, a coating structure of medical biodegradable zinc alloy stent and a preparation method thereof are published, the coating comprises three layers of S1, S2 and S3, S1 is an oxide coating, S2 is a polymer coating, and S3 is a drug coating.

Therefore, a treatment means which can provide a supporting force for a long time, has good adherence, is suitable for a nasal cavity special-shaped structure, has uniform and stable coating and good histocompatibility, prevents the support from falling off, keeps the nasal cavity unobstructed, effectively treats inflammation after the nasosinusitis operation and mucosa adhesion after the operation and effectively prevents the nasosinusitis from recrudescence is currently lacked clinically.

Disclosure of Invention

The invention aims to provide a degradable zinc alloy sinus stent which has excellent superplasticity, enables the stent to realize perfect adherence in a special nasal cavity, has good fixity, prevents the stent from falling off, keeps providing supporting force for a long time and keeps the nasal cavity smooth; the degradation products have no adverse effect on the organism and nasal passage tissues; the disease resistance of the organism can be enhanced, and the immunity of the organism can be improved; the synergistic effect of the drug coatings and the gradual release of the drugs solve the problems of inflammation, mucosa adhesion and the like after the nasosinusitis operation, and effectively prevent the recurrence of the nasosinusitis.

In order to achieve the purpose, the degradable zinc alloy sinus stent is characterized in that the alloy comprises the following components in percentage by mass: 0.001-5wt% of Fe, 0.001-10wt% of Mg, and 0-8wt% of Cu; the rest metal is Zn; is prepared by vacuum melting; adding Fe, mg and Cu in the smelting process to improve the mechanical property of the alloy; the surface of the bracket is coated with a coating and a high molecular drug; the alloy has good biological performance, and the degradation process and products are safe and effective to organisms and have treatment effect.

Preferably, the method is characterized in that metal powder is uniformly mixed according to a certain proportion, an alloy ingot is obtained by smelting in a vacuum smelting furnace, and the degradable zinc alloy sinus stent is obtained by heat treatment, extrusion heat treatment, drawing heat treatment and electrochemical polishing.

Preferably, the smelting temperature is 300-650 ℃, and the heat treatment temperature is 150-550 ℃.

Preferably, the first coating on the surface of the stent is an antibacterial metal compound, a frosted surface is provided, the particle size of the metal compound is 1-500nm, the coating thickness is 1-5 mu m, and the antibacterial metal compound is TiO ₂ And silver oxide.

Preferably, the surface of the stent is coated with high-molecular drugs such as anti-inflammatory drugs, analgesic drugs, antibacterial drugs, mucolytic drugs, and drugs for preventing and treating rhinitis.

Preferably, the drug coating may be selected from polyethylene glycol (PEG) or polylactic-2-glycolide (PLGA) or polyethylene-2-vinyl alcohol (EVAL) or polyethylene-2-vinyl acetate (EVA) coating polymers.

Preferably, the second coating on the surface of the stent is a medicament for preventing and treating rhinitis, such as: mometasone.

Preferably, the third coating on the surface of the stent is an anti-inflammatory analgesic drug, such as: dexamethasone and methylprednisolone.

Preferably, the fourth coating on the surface of the stent is an antibacterial drug, such as: doxycycline.

Preferably, the fifth coating on the surface of the stent is a mucolytic agent, such as: eucalyptus and pinene, and European and Roman drops.

Preferably, the thickness of each layer of the second to fifth coatings is 0-8 μm, and the density of each layer of the medicine is 0-25 μ g/mm ² 。

Preferably, the support structure is one or more of a long cylinder shape, a gourd shape and a sugarcoated gourd shape; the support structure is a combination of a long cylinder shape and a gourd shape, a combination of a long cylinder shape and a sugar gourd shape, and a combination of a long cylinder shape, a gourd shape and a sugar gourd shape.

Preferably, the diameter length of the stent is 5-180mm, the diameter is 3-40mm, and the grid of the stent structure is 2-20mm ² 。

Preferably, the maximum diameter position of the stent is: the diameter is more than or equal to 15mm, and the support structure grid is more than or equal to 5mm; minimum diameter position of stent: the diameter is more than or equal to 3mm, and the support structure grid is more than or equal to 2mm; compared with the position of the minimum diameter of the bracket, the position of the maximum diameter of the bracket has the large diameter which is not less than the small diameter, and the large grid which is not less than the small grid.

Preferably, the degradation period of the stent body in a human body is 1 to 3 years.

Compared with a sinus stent which can completely degrade high polymer materials, the polylactic acid material has low mechanical strength, and degradation products cause local aseptic inflammation; the zinc alloy material has high mechanical strength, and the degradation product has a therapeutic function as follows.

(1) The zinc can enhance the immunity of the human body and is also beneficial to the healing of wounds and wounds; the zinc ions generated by degradation can not cause apoptosis or necrosis of human endothelial cells and smooth muscle cells; the zinc degradation product ZnO is an astringent frequently used in clinic and has the functions of diminishing inflammation and relieving swelling; meanwhile, the zinc oxide also has good biocompatibility and antibacterial property.

(2) Magnesium is an activator and cofactor for various enzymes, and can catalyze the activation of enzymes and inhibit cell cycle, cell proliferation and differentiation.

(3) Iron can improve immunity, increase phagocytic function of neutrophil and phagocyte, and enhance anti-infection ability.

(4) The degradation product of copper has certain antibacterial effect.

(5) The alloy has good biological performance, can provide radial support effect for a long time, is safe and effective to organisms in a degradation process and a product, and can also play a role in preventing and treating diseases.

(6) According to the degradable zinc alloy nasal meatus stent, degradable zinc metal is used as a stent main body, the zinc metal material is high in mechanical strength and large in support, and a pipeline can be smoothly bent through a cavity.

(7) Silver can sterilize without damaging beneficial bacteria and normal cells, most pathogenic bacteria are unicellular microorganisms, which rely on protease to maintain metabolism and further propagate and influence normal cells, and an oxygen metabolism enzyme is also arranged in the proteases, when the silver meets the oxygen metabolism enzyme, an active group of the oxygen metabolism enzyme can rob away an electron of the silver, so that a silver atom is changed into a silver ion with positive charge, the silver ion can attract the specific combination of thiol groups (-SH) with negative charge in the protease to effectively pierce the cell wall and the outer surface of the cell membrane, and further the bacterial cells can not breathe, metabolize and propagate until the bacterial cells die due to the protein denaturation, thereby achieving the effect of sterilization.

(8) At pH >6, zinc alloys can be dissolved into zincate ions, a metabolizable form that is also incorporated as a cofactor in many human enzymes.

The invention has the advantages that: when the elongation of the zinc alloy exceeds 50%, the deformation capability of the bracket is very strong, and when the compliant balloon is expanded, the grid structure designs with different sizes and the superplasticity of the alloy ensure that the material is deformed and stressed uniformly and is tightly attached to the special-shaped nasal cavity; compared with other structural stents, the stent has the advantages that the outer part of the stent is a curve without edges and corners, the nasal cavity is prevented from being scratched in the process of releasing the stent, and irritation to the nasal cavity is reduced.

Drawings

FIG. 1 is a cross-sectional view of the stent of the present invention.

In the figure, 1 a zinc alloy stent, 2a metal compound coating, 3 a medicament for preventing and treating rhinitis, 4 an anti-inflammatory analgesic medicament, 5 an antibacterial medicament and 6 a mucolytic agent.

Detailed Description

The invention provides a degradable zinc alloy sinus stent which is characterized in that the alloy comprises the following components in percentage by mass: 0wt% -5wt% Fe, 0wt% -10wt% Mg and 0wt% -8wt% Cu; the rest metal is Zn; according to the mass percentage, the alloy elements are evenly mixed by a ball mill, then smelted in a vacuum smelting furnace, and the sinus stent is obtained by the working procedures of heat treatment, extrusion heat treatment, drawing heat treatment, cutting, shaping (if necessary), polishing, spraying and the like.

The present invention will be described more specifically with reference to the following examples, which are not intended to limit the scope of the present invention.

A zinc-magnesium alloy.

Example 1: the preparation process specifically comprises the following steps.

1. Ball milling: high-purity (99.999%) Zn and Mg powders (R.ltoreq.30 μm) were weighed in such a proportion that Mg was 0.6wt% and the balance Zn was. And (3) uniformly mixing the weighed powder in a high-energy ball mill (under a vacuum condition), wherein the mass ratio of the ball material is 10:1.

2. vacuum smelting: repeatedly vacuumizing, smelting the alloy at 300-650 ℃, cooling by cooling water for a period of time, and taking out the suction casting sample.

3. And (3) heat treatment: taking out the alloy, putting the alloy in a heating furnace, preserving the heat for 1 to 24 hours at the temperature of between 150 and 550 ℃, carrying out annealing treatment, and cooling along with the furnace.

4. Performing extrusion heat treatment and multiple slow-speed stretching heat treatment on the annealed alloy to obtain a diameter alloy bar, performing post-treatment, finally drawing to obtain a pipe with the diameter of about 1.5-20mm, and engraving and molding by a femtosecond laser cutting machine; the electrochemical polishing method removes impurities and edges and corners on the surface to make the surface smooth, and is intended to be used for nasal meatus stents.

5. And coating the first layer of antibacterial metal compound on the surface of the stent by a spraying or chemical deposition or electrochemical deposition method.

The zinc alloy material prepared by the method has the following medicine release speed: 0 percent.

Example 2: the difference between the embodiment and the specific example 1 is that a step 6 is added after the step 5, and finally a second layer of medicine is coated on the surface of the stent by a method of spraying or dipping and the like; the other steps and parameters were the same as in example 1.

The zinc alloy material prepared by the method has the following medicine release speed: releasing 73-83% in 1 month; releasing for 2 months at 85-92 percent; release 95-100% in 3 months.

Example 3: the difference between the embodiment and the specific example 2 is that a step 7 is added after the step 6, and finally a third layer of medicine is coated on the surface of the stent by a method of spraying or dipping and the like; the other steps and parameters were the same as in example 2.

The zinc alloy material prepared by the method has the following medicine release speed: releasing for 68 to 75 percent in 1 month; releasing for 83 to 90 percent in 2 months; releasing for 91-97% in 3 months.

Example 4: the difference between the embodiment and the specific example 3 is that a step 8 is added after the step 7, and finally a fourth layer of medicine is coated on the surface of the stent by a method of spraying or dipping and the like; the other steps and parameters were the same as in example 3.

The zinc alloy material prepared by the method has the following medicine release speed: releasing for 63 to 75 percent in 1 month; releasing for 80 to 88 percent in 2 months; 89 to 95% in 3 months.

Example 5: the difference between the embodiment and the specific example 4 is that a step 9 is added after the step 8, and a fifth layer of medicine is finally coated on the surface of the stent by a method of spraying or dipping and the like; the other steps and parameters were the same as in example 4.

The zinc alloy material prepared by the method has the following medicine release speed: releasing for 60 to 72 percent in 1 month; releasing for 74 to 85 percent in 2 months; release 86-92% in 3 months.

The corrosion rate of the zinc-magnesium alloy in a solution simulating the PH environment of the nasal cavity after being soaked for 30 days is as follows: 0.242 to 0.276mm/year; when the deformation rate is 10%, the radial support force of the bracket is 0.45-0.59N/mm; the tensile strength is 185 to 296Mpa; the radial retraction rate is 0.8 to 1.9 percent.

According to the first coating antibacterial metal compound, the frosted surface is provided by regulating and controlling the coatings with different particle sizes and thicknesses, so that the growth of tissues is facilitated, the first coating antibacterial metal compound can be better fused with the tissues, and the tissue compatibility is good; meanwhile, the first coating antibacterial metal compound is combined with the second coating to realize firm combination among the coatings, and the third coating is a transition coating, so that the coating cannot be damaged, cracked and detached in the deformation process of the bracket; the fourth coating is a coating with fast desorption and high diffusion coefficient; the fifth coating has large surface tension and good hydrophilicity, ensures the uniformity and stability of the coating, is beneficial to improving the growth of cells on the surface of the fifth coating and improves the histocompatibility of the material.

A zinc-iron alloy.

Example 6: alloy components: 0.53wt% of Fe and the balance of Zn, the steps and parameters of this embodiment being the same as those of specific example 1.

Example 7: alloy components: 0.53wt% of Fe and the balance of Zn, the steps and parameters of this embodiment being the same as those of specific example 2.

Example 8: alloy components: 0.53wt% of Fe and the balance of Zn, the steps and parameters of this embodiment being the same as those of specific example 3.

Example 9: alloy components: 0.53wt% Fe, the remainder being Zn, the steps and parameters of this embodiment being the same as those of specific example 4.

Example 10: alloy components: 0.53wt% Fe, the remainder being Zn, the steps and parameters of this embodiment being the same as those of specific example 5.

The corrosion rate of the zinc-iron alloy in a solution simulating the PH environment of the nasal cavity after being soaked for 30 days is as follows: 0.231 to 0.264 mm/year; when the deformation rate is 10%, the radial support force of the bracket is 0.47 to 0.64N/mm; the tensile strength is 168 to 273Mpa; the radial shrinkage is 1 to 2.1 percent.

A zinc-copper alloy.

Example 11: the alloy comprises the following components: 0.5wt% Cu, and the balance Zn, the steps and parameters of the present embodiment being the same as in specific example 1.

Example 12: alloy components: 0.5wt% of Cu and the balance of Zn, and the procedure and parameters of the present embodiment were the same as those of specific example 2.

Example 13: alloy components: 0.5wt% Cu, and the balance Zn, the steps and parameters of the present embodiment being the same as in specific example 3.

Example 14: alloy components: 0.5wt% of Cu and the balance of Zn, and the procedure and parameters of this embodiment were the same as those of specific example 4.

Example 15: alloy components: 0.5wt% of Cu and the balance of Zn, and the procedure and parameters of this embodiment are the same as those in specific example 5.

The corrosion rate of the zinc-copper alloy in a solution simulating the PH environment of the nasal cavity after being soaked for 30 days is as follows: 0.189 to 0.241mm/year; when the deformation rate is 10%, the radial support force of the bracket is 0.51 to 0.67N/mm; tensile strength is 184 to 267Mpa; the radial shrinkage rate is 1.6 to 2.6 percent.

A zinc-magnesium-copper alloy.

Example 16: alloy components: 2.0wt% of Cu,0.2wt% of Mg, and the balance of Zn, and the steps and parameters of the present embodiment are the same as those of specific example 1.

Example 17: alloy components: 2.0wt% of Cu,0.2wt% of Mg, and the balance of Zn, and the steps and parameters of the present embodiment are the same as those of specific example 2.

Example 18: alloy components: 2.0wt% of Cu,0.2wt% of Mg, and the balance of Zn, and the steps and parameters of the present embodiment are the same as those of specific example 3.

Example 19: alloy components: 2.0wt% of Cu,0.2wt% of Mg, and the balance of Zn, and the steps and parameters of the present embodiment were the same as those of specific example 4.

Example 20: alloy components: 2.0wt% Cu,0.2wt% Mg, the remainder being Zn, the steps and parameters of the present embodiment being the same as in specific example 5.

The corrosion rate of the zinc-magnesium-copper alloy in a solution simulating the pH environment of the nasal cavity after being soaked for 30 days is as follows: 0.163 to 0.219mm/year, and when the deformation rate is 10 percent, the radial support force of the stent is 0.57 to 0.69N/mm; the tensile strength is 172 to 306Mpa; the radial retraction rate is 2.1 to 3.8 percent.

A zinc-magnesium-iron alloy.

Example 21: alloy components: 0.3wt% of Fe,0.6wt% of Mg, and the balance of Zn, the steps and parameters of the present embodiment are the same as those of specific example 1.

Example 22: alloy components: 0.3wt% of Fe,0.6wt% of Mg, and the balance of Zn, the steps and parameters of the present embodiment are the same as those of specific example 2.

Example 23: the alloy comprises the following components: 0.3wt% of Fe,0.6wt% of Mg, and the balance of Zn, the steps and parameters of this embodiment are the same as those of specific example 3.

Example 24: alloy components: 0.3wt% of Fe,0.6wt% of Mg, and the balance of Zn, the steps and parameters of this embodiment are the same as those of specific example 4.

Example 25: alloy components: 0.3wt% of Fe,0.6wt% of Mg, and the balance of Zn, the steps and parameters of this embodiment are the same as those of specific example 5.

The corrosion rate of the zinc-magnesium-iron alloy in a solution simulating the pH environment of the nasal cavity after being soaked for 30 days is as follows: 0.182 to 0.249mm/year; when the deformation rate is 10%, the radial support force of the bracket is 0.60 to 0.72N/mm; the tensile strength is 203 to 316Mpa; the radial retraction rate is 1.3 to 2.9 percent.

A zinc-iron-copper alloy.

Example 26: alloy components: 0.3wt% of Fe,0.8wt% of Cu, and the balance of Zn, and the steps and parameters of this embodiment are the same as those of specific example 1.

Example 27: alloy components: 0.3wt% Fe,0.8wt% Cu, the remainder being Zn, the procedures and parameters of the present embodiment being the same as those in specific example 2.

Example 28: alloy components: 0.3wt% Fe,0.8wt% Cu, the remainder being Zn, the procedures and parameters of the present embodiment being the same as those in specific example 3.

Example 29: the alloy comprises the following components: 0.3% by weight of Fe, 0.8% by weight of Cu, and the balance of Zn, and the steps and parameters of this embodiment are the same as those of specific example 4.

Example 30: alloy components: 0.3% by weight of Fe, 0.8% by weight of Cu, and the balance of Zn, and the steps and parameters of this embodiment are the same as those of specific example 5.

The corrosion rate of the zinc-iron-copper alloy in a solution simulating the pH environment of the nasal cavity after being soaked for 30 days is as follows: 0.252 to 0.283mm/year; when the deformation rate is 10%, the radial support force of the bracket is 0.53 to 0.64N/mm; the tensile strength is 190 to 2458pa; the radial retraction rate is 1.5 to 3.5 percent.

A zinc-magnesium-iron-copper alloy.

Example 31: alloy components: 0.1wt% of Fe,0.7wt% of Cu,0.5wt% of Mg, and the balance of Zn, and the steps and parameters of the present embodiment are the same as those of specific example 1.

Example 32: alloy components: 0.1wt% Fe,0.7wt% Cu,0.5wt% Mg, the remainder being Zn, the steps and parameters of this embodiment being the same as in specific example 2.

Example 33: alloy components: 0.1wt% Fe,0.7wt% Cu,0.5wt% Mg, the remainder being Zn, the steps and parameters of this embodiment being the same as in specific example 3.

Example 34: the alloy comprises the following components: 0.1wt% of Fe,0.7wt% of Cu,0.5wt% of Mg, and the balance of Zn, and the steps and parameters of the present embodiment were the same as those of specific example 4.

Example 35: alloy components: 0.1wt% Fe,0.7wt% Cu,0.5wt% Mg, and the balance Zn, and the steps and parameters of the present embodiment were the same as those of specific example 5.

The corrosion rate of the zinc-magnesium-iron-copper alloy in a solution simulating the pH environment of the nasal cavity after being soaked for 30 days is as follows: 0.155 to 0.207mm/year; when the deformation rate is 10%, the radial support force of the bracket is 0.57 to 0.70N/mm; the tensile strength is 220 to 356Mpa; the radial retraction rate is 2.4 to 3.9 percent.

Example 36: zinc-copper alloy: the alloy material contains 0.5wt% of copper and the balance of zinc, and the elongation of the alloy material is 103%.

Example 37: zinc-copper alloy: the copper alloy material contains 0.9wt% of copper and the balance of zinc, and the elongation of the alloy material is 198%.

Example 38: zinc-copper alloy: the alloy material contains 1.5wt% of copper and the balance of zinc, and the elongation of the alloy material is 141%.

Example 39: zinc-iron-copper alloy: the alloy material contains 0.3wt% of iron, 0.8wt% of copper and the balance of zinc, and the elongation of the alloy material is 95%.

Example 40: zinc-iron-copper alloy: the alloy material contains 0.5wt% of iron, 0.8wt% of copper and the balance of zinc, and the elongation of the alloy material is 106%.

Example 41: zinc-iron-copper alloy: the alloy material contains 0.5wt% of iron, 1.0wt% of copper and the balance of zinc, and the elongation of the alloy material is 113%.

Example 42: zinc-magnesium-copper alloy: the alloy material contains 0.2wt% of magnesium, 2.0wt% of copper and the balance of zinc, and the elongation of the alloy material is 83%.

Example 43: zinc-iron-magnesium alloy: the alloy material contains 0.3wt% of iron, 0.6wt% of magnesium and the balance of zinc, and the elongation of the alloy material is 90%.

Example 44: zinc-iron-magnesium alloy: the alloy material contains 4.3wt% of iron, 8.6wt% of magnesium and the balance of zinc, and the elongation of the alloy material is 56%.

Example 45: zinc-iron-magnesium alloy: the alloy material contains 0.005wt% of iron, 0.009wt% of magnesium and the balance of zinc, and the elongation of the alloy material is 60%.

Example 46: zinc-iron-magnesium alloy: the alloy material contains 2.1wt% of iron, 4.8wt% of magnesium and the balance of zinc, and the elongation of the alloy material is 115%.

Example 47: zinc-iron-copper-magnesium alloy: the alloy material contains 0.1wt% of iron, 0.7wt% of copper, 0.5wt% of magnesium and the balance of zinc, and the elongation of the alloy material is 63%.

Example 48: zinc-iron-copper-magnesium alloy: the alloy material contains 0.003wt% of iron, 0.005wt% of copper, 0.005wt% of magnesium and the balance of zinc, and the elongation of the alloy material is 59%.

Example 49: zinc-iron-copper-magnesium alloy: the alloy material contains 4.0wt% of iron, 7.0wt% of copper, 8.8wt% of magnesium and the balance of zinc, and the elongation of the alloy material is 54%.

Example 50: zinc-iron-copper-magnesium alloy: the alloy material contains 2.3wt% of iron, 3.7wt% of copper, 4.5wt% of magnesium and the balance of zinc, and the elongation of the alloy material is 98%.

Comparative example 1: zinc-iron-copper alloy: the zinc-based alloy implant material prepared according to the method of the embodiment 1 of the invention contains 10.0wt% of iron, 2.0wt% of copper and the balance of zinc, the total content of impurities is less than 0.001wt%, and the elongation is 12%.

Comparative example 2: zinc-iron-copper alloy: the zinc-based alloy implant material prepared according to the method of the embodiment 1 of the invention contains 12.0wt% of iron, 3.0wt% of copper and the balance of zinc, the total content of impurities is less than 0.001wt%, and the elongation is 19%.

Comparative example 3: zinc-iron alloy: the zinc-based alloy implant material prepared by the method of the embodiment 1 of the invention contains 12wt% of iron and the balance of zinc, the total impurity content is less than 0.001%, and the elongation is 13%.

Comparative example 4: zinc-iron alloy: the zinc-based alloy implant material prepared by the method of the embodiment 1 of the invention contains 10wt% of iron and the balance of zinc, the total impurity content is less than 0.001%, and the elongation is 15%.

The example results show that the degradable zinc-based alloy implant material of the invention can meet the requirements of the material implant body for supporting and processing performance no matter the mechanical strength (tensile strength), the elongation performance (elongation percentage) and the radial supporting force and the radial retraction rate of the bracket when the deformation rate is 10 percent; in addition, the material has ideal degradation speed (corrosion speed) (0.15 mm/a-0.45 mm/a), and can be used as a degradable in-vivo implant material; among the 7 alloys, researches show that the Zn-Fe-Mg-Cu alloy has the slowest corrosion rate, can provide a supporting force for a long time and has the fastest corrosion rate; when the deformation is 10%, the radial supporting force of the Zn-Fe-Mg alloy and the Zn-Fe-Mg-Cu alloy bracket is excellent, the radial supporting force of the Zn-Mg alloy bracket is minimum, and the tensile strength of the Zn-Fe-Mg alloy and the Zn-Fe-Mg-Cu alloy is better than that of other 5 alloys.

Compared with the zinc-based alloy implant material, researches show that when the elongation is more than 50%, the deformation capacity of the bracket is very strong, and the bracket is easily attached to the special nasal cavity according to the contour change of the nasal cavity by combining the grid structure design with different sizes in the supporting process of the bracket. The elongation of the material of the comparative example is too low, so that the material is high in brittleness, the processing of the bracket micro-tube is not facilitated, and the material is not easy to deform in the deformation process and is not suitable for a special-shaped cavity.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims

1. A degradable zinc alloy nasal sinus support is characterized in that the alloy comprises the following components in percentage by mass: 0.001 to 5wt% Fe, 0.001 to 10wt% Mg and 0 to 8wt% Cu; the rest metal is Zn; preparing zinc-based alloy through vacuum melting, and preparing the supports with different structures through post processing; the support structure is one or more of a long cylinder, a calabash shape and a sugarcoated haw shape; maximum diameter position of the stent: the diameter is more than or equal to 15mm, and the support structure grid is more than or equal to 5mm; minimum diameter position of stent: the diameter is more than or equal to 3mm, and the support structure grid is more than or equal to 2mm; compared with the position with the minimum diameter of the bracket, the position with the maximum diameter of the bracket has the large diameter which is more than or equal to the small diameter, and the position with the large grid which is more than or equal to the small grid; the surface of the bracket is coated with a coating and a high molecular drug; a conveying system is arranged in the stent, and the balloon used by the conveying system is a compliance balloon; the zinc alloy is characterized in that the elongation of the zinc alloy material exceeds 50 percent.

2. The degradable zinc alloy sinus stent of claim 1, wherein the purity of Zn, fe, mg, cu is greater than 99.999% and the radius of the metal powder is less than 30 μm.

3. The degradable zinc alloy sinus stent of claim 1, wherein the first coating on the surface of the stent is an antibacterial metallic compound and provides a frosted surface, the metallic compound has a particle size of 1-500nm and a coating thickness of 1-5 μm, and the antibacterial metallic compound is TiO ₂ And silver oxide.

4. The degradable zinc alloy sinus stent of claim 3, wherein the second coating on the surface of the stent is a drug for preventing and treating rhinitis, the third coating is an anti-inflammatory analgesic drug, the fourth coating is an antibacterial drug, and the fifth coating is a mucolytic agent.

5. The degradable zinc alloy sinus stent of claim 4, wherein the second to fifth coatings each have a thickness of 0-8 μm and a drug density of 0-25 μ g/mm ² 。

6. The degradable zinc alloy sinus stent of claim 1, wherein the stent has a diameter of 5-180mm in length, a diameter of 3-40mm, and a lattice of 2-20mm in the structure of the stent ² 。