Developable absorbable nail for repairing and fixing ligament around ankle joint and preparation method of developable absorbable nail
By chemically bonding the iodine-containing compound with polymer materials, absorbable nails with X-ray autodevelopment capabilities were prepared, which solved the problem that absorbable nails in the prior art are difficult to develop under X-ray, and the clear observation of the position and the broken nails are achieved, and physiological toxicity is avoided.
Patent Information
- Application Number
- CN202510449045.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-10
- Publication Date
- 2025-08-01
AI Technical Summary
The existing absorbable nails are difficult to develop under X-ray, and their position and nail breakage cannot be accurately observed.
By chemically bonding the iodine-containing compound to the polymer material, absorbable nails with X-ray autodevelopment capabilities were prepared, and the high absorption of the iodine element was used to develop under X-ray.
The absorption nail is developed under X-ray, ensuring clear observation of the absorbable nail position and the broken nail condition, and avoiding the physiological toxicity of heavy metal salts.
Smart Images
Figure CN120393130A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of bone nails, and particularly relates to a radiopaque absorbable nail for repairing and fixing ankle ligaments and a preparation method thereof. Background Art
[0002] Ankle sprain is a very common ankle injury, mostly occurring in sports. Although most ankle sprains can recover, about 20% of patients will still experience chronic ankle instability, which leads to persistent pain, reduced physical activity, decreased quality of life, and may cause degenerative changes in the ankle joint. Most ankle injuries involve the lateral ligaments, including the anterior talofibular ligament (ATFL), the calcaneofibular ligament (CFL), and the posterior talofibular ligament (PTFL). Among them, the ATFL is the weakest part of the lateral ankle ligaments, so ankle injuries mostly occur in the ATFL. Taking the rupture of the ATFL as an example, the currently commonly used operation is arthroscopic-assisted ligament repair. That is, a hole is drilled in the fibula in advance to provide an access channel, and then an absorbable nail is implanted into the reserved channel. The screw thread around the nail is used to combine with the fibula to achieve fixation, and the rope on the nail is knotted with the ruptured anterior talofibular ligament to achieve the repair of the ATFL.
[0003] Currently, the absorbable nails used in China are mainly imported. It is difficult to visualize them under X-ray during and after the operation. Only a faint translucent shadow of the nail track can be observed, and the position of the absorbable nail cannot be accurately observed. Summary of the Invention
[0004] The technical problem to be solved by the present invention is to provide a radiopaque absorbable nail for repairing and fixing ankle ligaments and a preparation method thereof, which can solve the problem that the absorbable nail is difficult to visualize under X-ray after being implanted into the human body, so as to more clearly observe the position of the absorbable nail and timely observe the situation of broken nails.
[0005] The present invention provides a radiopaque absorbable nail for repairing and fixing ankle ligaments, which is obtained by combining an iodine-containing compound with a screw body through a polymer functional method.
[0006] Further, the polymer functional method refers to introducing an iodine-containing compound into the polymer chain of the screw body in a chemical bonding manner to obtain a functionalized material with X-ray autoradiography ability.
[0007] Preferably, the iodine-containing compound is one or more of diiodoneopentyl glycol, iodoethylene glycol, iodoethylenediamine, iodobutanediol, and iodobutanediamine.
[0008] Preferably, the material of the screw body is a composite material of hydroxyapatite and polylactic acid. Hydroxyapatite has good biocompatibility with the human body, can bind to bone, and can be used as a bone substitute material; polylactic acid has good biocompatibility and degradation performance. Mixing the two to prepare a composite can obtain a polymer material with better comprehensive performance.
[0009] The present invention also provides a preparation method of a radiopaque absorbable screw for repairing and fixing ankle ligaments, comprising the following steps: (1) Dissolve dibromoneopentyl glycol in a solvent, then add an excessive amount of iodine-containing compound, stir well to dissolve, heat and reflux, evaporate the solvent by rotary evaporation, wash, and dry to obtain diiodoneopentyl glycol; (2) Mix the above-mentioned diiodoneopentyl glycol, L-lactide, and hydroxyapatite, and react at 140 - 150 °C for 5 - 10 h under the action of a catalyst, and obtain the absorbable screw after purification and drying.
[0010] Preferably, the mass-volume ratio of dibromoneopentyl glycol to the solvent in step (1) is 1 g:2 mL - 1 g:20 mL.
[0011] Preferably, the solvent in step (1) is acetone.
[0012] Preferably, the heating temperature in step (1) is 60 - 160 °C; the reflux time is 60 - 70 h.
[0013] Preferably, the molar ratio of diiodoneopentyl glycol to L-lactide in step (2) is 0.1 - 1:100.
[0014] Preferably, the addition amount of hydroxyapatite in step (2) is 5 - 10% of the total mass of diiodoneopentyl glycol and L-lactide.
[0015] Preferably, the catalyst in step (2) is stannous octoate, and its mass ratio to diiodoneopentyl glycol is 0.5:1000 - 5:1000.
[0016] In the present invention, iodine element can meet the requirement of "invisibility" of the contrast agent in pharmacology due to its high absorbability to X-rays and relative inertness, that is, it will not show any pharmacological activity in the organism, so the disadvantages of large physiological toxicity of heavy metal salts to the human body can be avoided.
[0017] By chemically bonding iodine-containing small molecules to the polymer chain, a functional material with X-ray autoradiography ability is obtained to acquire an X-ray autoradiographic polymer material with stable imaging performance and low physiological toxicity. Compared with the ionic bond of heavy metal salts, iodine atoms have lower biological toxicity, and their bonding mode with polymers is usually a more stable covalent bond. Therefore, introducing iodine-containing compounds can obtain an X-ray autoradiographic polymer material with more stable imaging performance. The molecular chain of the polylactic acid material is usually capped with hydroxyl groups. The more the number of chain-end hydroxyl groups, the more chain-end functionalization reaction active sites are available for introducing imaging groups.
[0018] Beneficial effects Based on the traditional polymer material ankle ligament repair fixation nail, the present invention combines the polymer material with iodine-containing compounds by polymer functionalization method to achieve the effect of imaging under X-ray. The present invention can solve the problem that the absorbable nail is difficult to image under X-ray after being implanted into the human body, so as to more clearly observe the position of the absorbable nail and timely observe the situation of broken nails. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 It is a schematic diagram of the absorbable nail of the present invention. DETAILED DESCRIPTION OF THE INVENTION
[0020] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.
[0021] Example 1 This example provides a preparation method of an absorbable nail for repairing and fixing ankle ligaments that can be imaged, including the following steps: (1) Dissolve 5 g of dibromoneopentyl glycol in 10 mL of acetone, then add an excessive amount of iodine-containing compound, stir well to dissolve, heat and reflux for 72 h, then rotary evaporate to remove the solvent, wash with water three times, take the organic phase to obtain a solution of diiodoneopentyl glycol, rotary evaporate, and dry to obtain diiodoneopentyl glycol.
[0022] (2) Mix the above-mentioned diiodoneopentyl glycol, L-lactide (molar ratio 0.33:100) and hydroxyapatite (5% of the total mass of diiodoneopentyl glycol and L-lactide), and react at 140 °C for 7 h under the action of catalyst stannous octoate (1‰), and obtain the absorbable nail after purification and drying.
[0023] Example 2 This embodiment provides a preparation method of an X-ray visible absorbable nail for repairing and fixing ankle ligaments, comprising the following steps: (1) Dissolve 5 g of 2,2-bis(bromomethyl)-1,3-propanediol in 20 mL of acetone, then add an excessive amount of iodine-containing compound. After fully stirring and dissolving, heat and reflux for 72 h. Then, remove the solvent by rotary evaporation and wash with water three times. Take the organic phase to obtain the 2,2-bis(iodomethyl)-1,3-propanediol solution. After rotary evaporation and drying, 2,2-bis(iodomethyl)-1,3-propanediol is obtained.
[0024] (2) Mix the above-mentioned 2,2-bis(iodomethyl)-1,3-propanediol, L-lactide (molar ratio of 0.5:100) and hydroxyapatite (5% of the total mass of 2,2-bis(iodomethyl)-1,3-propanediol and L-lactide), and react at 140 °C for 7 h under the action of the catalyst stannous octanoate (1‰). After purification and drying, the absorbable nail is obtained.
[0025] Example 3 This embodiment provides a preparation method of an X-ray visible absorbable nail for repairing and fixing ankle ligaments, comprising the following steps: (1) Dissolve 5 g of 2,2-bis(bromomethyl)-1,3-propanediol in 50 mL of acetone, then add an excessive amount of iodine-containing compound. After fully stirring and dissolving, heat and reflux for 72 h. Then, remove the solvent by rotary evaporation and wash with water three times. Take the organic phase to obtain the 2,2-bis(iodomethyl)-1,3-propanediol solution. After rotary evaporation and drying, 2,2-bis(iodomethyl)-1,3-propanediol is obtained.
[0026] (2) Mix the above-mentioned 2,2-bis(iodomethyl)-1,3-propanediol, L-lactide (molar ratio of 0.8:100) and hydroxyapatite (5% of the total mass of 2,2-bis(iodomethyl)-1,3-propanediol and L-lactide), and react at 140 °C for 7 h under the action of the catalyst stannous octanoate (1‰). After purification and drying, the absorbable nail is obtained.
[0027] Based on the traditional polymer material ankle ligament repair and fixation nail, the present invention combines the polymer material with an iodine-containing compound by polymer functionalization method, so as to achieve the effect of X-ray imaging. The present invention can solve the problem that the absorbable nail is difficult to be imaged under X-ray after being implanted into the human body, so as to more clearly observe the position of the absorbable nail and timely observe the situation of broken nails.
Claims
1. A developable absorbable nail for repairing and fixing ankle ligaments, characterized in that: The absorbable nail is obtained by combining an iodine-containing compound and a screw body through a polymer functional method.
2. The absorbable nail according to claim 1, wherein: The polymer functional method refers to introducing an iodine-containing compound into the polymer chain of the screw body by means of chemical bonding to obtain a functional material with X-ray autoradiography ability.
3. The absorbable nail according to claim 1, wherein: The iodine-containing compound is one or more of dibromo neopentyl glycol, iodoethylene glycol, iodoethylenediamine, iodobutanediol, and iodobutanediamine.
4. The absorbable nail according to claim 1, wherein: The material of the screw body is a composite material of hydroxyapatite and polylactic acid.
5. A preparation method of a developable absorbable nail for repairing and fixing ankle ligaments, comprising the following steps: (1) Dissolve dibromo neopentyl glycol in a solvent, then add an excessive amount of iodine-containing compound, stir well to dissolve, heat and reflux, evaporate the solvent by rotary evaporation, wash, and dry to obtain dibromo neopentyl glycol; (2) Mix the above dibromo neopentyl glycol, L-lactide, and hydroxyapatite, and react at 140-150°C for 5-10 h under the action of a catalyst, and obtain the absorbable nail after purification and drying.
6. The preparation method according to claim 5, characterized in that: The mass-volume ratio of dibromo neopentyl glycol to the solvent in step (1) is 1 g: 2 mL - 1 g: 20 mL.
7. The preparation method according to claim 5, wherein: The solvent in step (1) is acetone.
8. The preparation method according to claim 5, wherein: The heating temperature in step (1) is 60-160°C; the reflux time is 60-70 h.
9. The preparation method according to claim 5, characterized in that: The molar ratio of dibromo neopentyl glycol to L-lactide in step (2) is 0.1-1:
100.
10. The preparation method according to claim 5, characterized in that: The catalyst in step (2) is stannous octoate, and its mass ratio to dibromo neopentyl glycol is 0.5: 1000 - 5: 1000.