A degradable tourniquet with reinforced structure and a preparation method thereof
By introducing a base layer of biodegradable epoxy resin and nano-titanium dioxide mixture into the tourniquet and adding honeycomb-shaped reinforcing ribs, the problems of difficult degradation and insufficient elasticity of rubber tourniquets are solved, and a tourniquet with high elasticity and rapid degradation is achieved.
Patent Information
- Application Number
- CN202510922067.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-04
- Publication Date
- 2026-02-03
- Estimated Expiration
- 2045-07-04
AI Technical Summary
Existing rubber tourniquets are difficult to degrade, leading to difficulties in the disposal of medical waste rubber. At the same time, the elastic properties of degradable polymer materials cannot meet the high elasticity requirements of tourniquets.
The biodegradable tourniquet with a reinforced structure includes a base layer and a reinforcing rib layer. The base layer is formed of a mixture of biodegradable epoxy resin and nano-titanium dioxide. Reinforcing ribs are added to improve elasticity and tensile strength. The ribs adopt a honeycomb structure to distribute stress.
It achieves good degradation performance and high elasticity of tourniquet, meeting the requirements of lightweight and degradability. The honeycomb structure improves tensile strength and degradation rate.
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Figure CN120617595B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of tourniquet preparation technology, and specifically relates to a biodegradable tourniquet with a reinforced structure and its preparation method. Background Technology
[0002] The tourniquet is made of medical-grade polymer material, is long and flat, and highly elastic. It is suitable for single-use use in medical institutions for routine treatment and rescue procedures such as intravenous infusion, blood drawing, and blood transfusion, or for emergency hemostasis of limb bleeding or bleeding from snake and insect bites in the wild.
[0003] The most common type of tourniquet on the market is the rubber tourniquet. As rubber tourniquets are no longer used, they become medical waste rubber. Rubber is difficult to degrade, ultimately leading to the problem of difficult disposal of medical waste rubber.
[0004] However, when biodegradable polymers are used as raw materials for tourniquets, their elastic properties cannot meet the high elasticity requirements of tourniquets. Therefore, how to manufacture a biodegradable tourniquet and its preparation method are urgent problems to be solved. Summary of the Invention
[0005] To address the above problems, this invention provides a biodegradable tourniquet with a reinforced structure and its preparation method.
[0006] The first objective of this invention is achieved through the following technical solution:
[0007] A biodegradable tourniquet with a reinforced structure includes: a base layer and a reinforcing rib layer; the reinforcing rib layer is disposed on the outer side of the base layer;
[0008] The base layer comprises the following raw materials in parts by weight: 50-80 parts polyethylene, 20-50 parts accelerator;
[0009] The accelerator is obtained by mixing and granulating a biodegradable epoxy resin, an epoxy silane coupling agent, and nano-titanium dioxide.
[0010] The reinforcing rib layer includes several reinforcing ribs disposed on the base layer.
[0011] Furthermore, the reinforcing ribs of the reinforcing rib layer are mesh-like, diagonal-patterned, or honeycomb-like.
[0012] Furthermore, the mass ratio of the biodegradable epoxy resin, epoxy silane coupling agent, and nano titanium dioxide is 55-70:1.2-3:30-45, the mixing temperature is 50-70℃, and the mixing time is 10-30 min.
[0013] Furthermore, the biodegradable epoxy resin is prepared by hyperbranching and epoxidative end-capping of biodegradable triol and 1,6-adipic acid.
[0014] Furthermore, the hyperbranching reaction conditions are as follows: under the action of the first organic solvent and the esterification reaction catalyst, the temperature is 90-150℃, the time is 4-8h, and the molar ratio of the degradable triol to 1,6-adipic acid is 2-3:3.
[0015] Preferably, to obtain hyperbranched reaction products with higher branching degree, the hyperbranching reaction includes:
[0016] After thoroughly mixing the biodegradable triol, 1,6-adipic acid, and DMF, concentrated sulfuric acid was added dropwise with stirring. Once the addition was complete, the mixture was heated to 90-110°C and stirred continuously for 1-2 hours. The temperature was then raised to 120-150°C and stirred continuously for 2-3 hours. The reaction was then stopped, and the hyperbranched product was obtained after post-treatment.
[0017] Furthermore, the first organic solvent is one of N,N-dimethylformamide (DMF), benzene, and toluene.
[0018] Furthermore, the catalyst for the esterification reaction is one of concentrated sulfuric acid and p-toluenesulfonic acid.
[0019] Furthermore, the epoxidation end-capping reaction is a reaction between the hyperbranching reaction product and epichlorohydrin;
[0020] The epoxidation end-capping reaction includes:
[0021] The hyperbranched reaction product and epichlorohydrin were heated to reflux for 4-8 hours. Then, a second organic solvent and NaOH were added, and the mixture was heated to 50-55°C and stirred for 4-8 hours. The reaction was then stopped, and the product was post-treated to obtain a biodegradable epoxy resin.
[0022] Furthermore, the second organic solvent is one of chloroform, N,N-dimethylformamide (DMF), and toluene.
[0023] Furthermore, the biodegradable triol is made from p-hydroxyaniline and formaldehyde; the molar ratio of p-hydroxyaniline to formaldehyde is 1:3-3.2; the reaction conditions for p-hydroxyaniline and formaldehyde are: in a third organic solvent, at a temperature of 50-70°C, and for a reaction time of 5-8 hours.
[0024] Furthermore, the third organic solvent is one of ethanol, chloroform, and N,N-dimethylformamide (DMF).
[0025] Preferably, the reaction for obtaining the degradable triol includes:
[0026] After mixing formaldehyde aqueous solution (37% by mass), p-hydroxyaniline and a third organic solvent evenly, the mixture is heated to 50-70℃ and kept at this temperature with stirring for 5-8 hours. The mixture is then rotary evaporated to obtain a biodegradable triol.
[0027] The molecular structure of the biodegradable triol is shown below.
[0028]
[0029] In this invention, processing aids (lubricants, etc.) and antioxidants are added to the raw materials of the tourniquet according to the processing performance or antioxidant performance of the tourniquet.
[0030] The processing aids and antioxidants mentioned are processing aids and antioxidants of resins in this technical field, and are not specifically limited in this invention.
[0031] Furthermore, the reinforcing rib comprises the following raw materials in parts by weight: 55-65 parts polylactic acid, 25-35 parts polycaprolactone, 5-10 parts nano hydroxyapatite, 8-12 parts polyethylene glycol (Mw=4000-6000), and 3-5 parts triethyl citrate.
[0032] Furthermore, the reinforcing ribs are made of SEBS material.
[0033] The second objective of this invention is achieved through the following technical solution:
[0034] A method for preparing a biodegradable tourniquet, comprising:
[0035] After the polyethylene and accelerator are melt-mixed, they are extruded and molded to obtain the base layer of the biodegradable tourniquet;
[0036] The reinforcing ribs are placed on the outside of the base layer of the biodegradable tourniquet and then laminated using a hot press laminating machine to obtain a biodegradable tourniquet with a reinforcing rib layer.
[0037] The beneficial effects of this invention are:
[0038] This invention discloses a biodegradable tourniquet. By introducing an accelerator into polyethylene, wherein the accelerator is a biodegradable epoxy resin and nano-titanium dioxide melt-blended and extruded into granules, the introduction of the accelerator not only utilizes the photocatalytic degradation effect of nano-titanium dioxide on polyethylene, but also utilizes the toughening and self-curing properties of the biodegradable epoxy resin to form an interpenetrating network, giving the final composite good degradation and elastic properties; and the addition of a reinforcing rib structure improves the tensile strength of the tourniquet.
[0039] The reinforcing rib structure is preferably honeycomb-shaped. The honeycomb structure can effectively disperse stress and avoid stress concentration that could lead to localized tearing. It also has high tensile strength for the same mass, meeting the requirements for lightweighting. Furthermore, the honeycomb mesh structure has interconnected channels, which can improve the degradation rate of the tourniquet and meet the requirements for biodegradability.
[0040] Significantly, the biodegradable epoxy resin in this invention is a biodegradable hyperbranched epoxy resin, and the hyperbranched structure provides a large amount of loading space for nano-titanium dioxide.
[0041] Secondly, the biodegradable epoxy resin in this invention contains a triazine ring and a biodegradable ester group. The ester group can be rapidly degraded by heating in an organic solvent, and the triazine ring can be rapidly degraded in an organic solvent (such as DMF) under heating (80-100℃) and / or catalyst (acidic or alkaline) conditions.
[0042] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. Attached Figure Description
[0043] Figure 1 This is a schematic diagram of the structure of the biodegradable tourniquet provided in the embodiments of this application. Detailed Implementation
[0044] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0045] This application provides a biodegradable tourniquet 1 with a reinforced structure. The biodegradable tourniquet 1 includes a base layer 12 and a reinforcing rib layer 11. The reinforcing rib layer 11 includes a plurality of reinforcing ribs disposed on the base layer.
[0046] Optionally, the reinforcing ribs can be arranged at intersections.
[0047] Optionally, the reinforcing ribs of the reinforcing rib layer are mesh-like, diagonal-patterned, or honeycomb-like.
[0048] Optionally, an anti-slip layer 13 is provided on the inner side of the base layer 12, the anti-slip layer 13 being used to enhance friction during contact. The anti-slip layer 13 may be an anti-slip pattern.
[0049] Optionally, the reinforcing ribs comprise the following raw materials in parts by weight: 55-65 parts polylactic acid, 25-35 parts polycaprolactone, 5-10 parts nano-hydroxyapatite, 8-12 parts polyethylene glycol (Mw=4000-6000), and 3-5 parts triethyl citrate. A balance of rigidity and toughness is achieved through the PLA / PCL biphase system (55-65 parts rigid PLA + 25-35 parts flexible PCL). Nano-hydroxyapatite (5-10 parts) forms stress-enhancing points at the honeycomb nodes, improving compressive strength. The high hydrophilicity of polyethylene glycol (8-12 parts) accelerates liquid penetration and promotes uniform hydrolytic degradation. Triethyl citrate (3-5 parts) synergistically reduces melt viscosity with polyethylene glycol, ensuring the integrity of the injection molding of complex honeycomb structures.
[0050] Optionally, the reinforcing ribs are made of bio-based TPE material. The manufacturing methods and processes of TPE material are existing technologies and will not be elaborated on here.
[0051] Optionally, the reinforcing ribs are made of SEBS material. Specifically, SEBS is a linear triblock copolymer with polystyrene as the end segment and ethylene-butene copolymer obtained by hydrogenating polybutadiene as the middle elastic block. SEBS does not contain unsaturated double bonds, thus exhibiting good stability and aging resistance.
[0052] Wherein, when the reinforcing ribs of this application are honeycomb-shaped, such as Figure 1 As shown, the honeycomb mesh reinforcing ribs include at least two layers of honeycomb mesh structure, thereby enhancing tensile strength.
[0053] The following examples illustrate and test a biodegradable tourniquet with two layers of honeycomb mesh reinforcing ribs.
[0054] Example 1
[0055] Preparation of biodegradable epoxy resin:
[0056] A1. Mix 0.3 mol of formaldehyde aqueous solution (37% by mass), 0.1 mol of p-hydroxyaniline and 150 mL of ethanol evenly, heat to reflux and stir for 5 h, rotary evaporate, and purify by column chromatography to obtain a biodegradable triol.
[0057] A2. Mix 0.22 mol of biodegradable triol, 0.3 mol of 1,6-adipic acid, and 300 mL of DMF until homogeneous. Add concentrated sulfuric acid (98% by mass, 1.5% of the total mass of the biodegradable triol and 1,6-adipic acid) dropwise while stirring. After complete addition, heat to 110°C and stir continuously for 1 hour. Increase the temperature to 140°C and stir continuously for 2 hours. Stop the reaction, evaporate by rotary evaporation, wash with water, and dry to obtain the hyperbranched reaction product. Heat the obtained hyperbranched reaction product and epichlorohydrin (excess, 0.9 mol in this example) to reflux for 4 hours. Remove excess epichlorohydrin by rotary evaporation. Add 300 mL of DMF and excess NaOH (1 mol in this example), heat to 50°C, stir for 4 hours, evaporate by rotary evaporation, wash with water, take the organic layer, and dry to obtain the biodegradable epoxy resin.
[0058] Example 2
[0059] Preparation of biodegradable epoxy resin:
[0060] A1. Mix 0.32 mol of formaldehyde aqueous solution (mass fraction 37%), 0.1 mol of p-hydroxyaniline and 150 mL of ethanol evenly, heat to reflux and stir for 5-8 h, rotary evaporate, and purify by column chromatography to obtain degradable triol.
[0061] A2. Mix 0.3 mol of biodegradable triol, 0.3 mol of 1,6-adipic acid, and 300 mL of DMF until homogeneous. Add concentrated sulfuric acid (98% by mass, 1.5% of the total mass of the biodegradable triol and 1,6-adipic acid) dropwise while stirring. After complete addition, heat to 90°C and stir continuously for 2 hours. Increase the temperature to 120°C and stir continuously for 3 hours. Stop the reaction, evaporate by rotary evaporation, wash with water, and dry to obtain the hyperbranched reaction product. Heat the obtained hyperbranched reaction product and epichlorohydrin (excess, 0.9 mol in this example) to reflux for 8 hours. Remove excess epichlorohydrin by rotary evaporation. Add 300 mL of DMF and excess NaOH (1 mol in this example), heat to 55°C, stir for 8 hours, evaporate by rotary evaporation, wash with water, collect the organic layer, and dry to obtain the biodegradable epoxy resin.
[0062] Example 3
[0063] Preparation of accelerators:
[0064] 70g of the biodegradable epoxy resin prepared in Example 1, 1.2g of epoxy silane coupling agent and 30g of nano titanium dioxide were mixed at 70°C for 15min and then extruded to granulate to obtain the accelerator.
[0065] Example 4
[0066] Preparation of accelerators:
[0067] 55g of the biodegradable epoxy resin prepared in Example 2, 3g of epoxy silane coupling agent and 45g of nano titanium dioxide were mixed at 50°C for 30min and then extruded to granulate to obtain the accelerator.
[0068] Example 5
[0069] Preparation of biodegradable tourniquet base layer:
[0070] After melting and mixing 80 parts by weight of polyethylene and 20 parts by weight of the accelerator prepared in Example 4, the mixture is extruded and molded to obtain a biodegradable tourniquet base layer. The melting and mixing temperature is 150-170°C and the extrusion temperature is 180-230°C.
[0071] Example 6
[0072] Preparation of biodegradable tourniquet base layer:
[0073] After 65 parts by weight of polyethylene and 35 parts by weight of the accelerator prepared in Example 4 were melt-mixed, the mixture was extruded and molded to obtain a biodegradable tourniquet base layer. The melt mixing temperature was 150-170°C and the extrusion temperature was 180-230°C.
[0074] Example 7
[0075] Preparation of biodegradable tourniquet base layer:
[0076] After 50 parts by weight of polyethylene and 50 parts by weight of the accelerator prepared in Example 4 were melt-mixed, the mixture was extruded and molded to obtain a biodegradable tourniquet base layer. The melt mixing temperature was 150-170°C and the extrusion temperature was 180-230°C.
[0077] Example 8
[0078] Preparation of honeycomb mesh reinforcing ribs:
[0079] Weigh out 55 parts of polylactic acid, 25 parts of polycaprolactone, 5 parts of nano hydroxyapatite, 8 parts of polyethylene glycol (Mw = 4000) and 3 parts of triethyl citrate, add them to a high-speed mixer and mix at 60°C for 15 minutes.
[0080] The mixed raw materials are added to a twin-screw extruder, the extrusion temperature is controlled at 160℃, the screw speed is 100r / min, and the extruded strips are then pelletized.
[0081] The granules are placed into an injection molding machine and molded using a honeycomb mesh mold at an injection temperature of 170℃ and a pressure of 80MPa to obtain honeycomb mesh reinforcing ribs.
[0082] Example 9
[0083] Preparation of honeycomb mesh reinforcing ribs:
[0084] Weigh out 65 parts of polylactic acid, 35 parts of polycaprolactone, 10 parts of nano hydroxyapatite, 12 parts of polyethylene glycol (Mw = 6000) and 5 parts of triethyl citrate, add them to a high-speed mixer and mix at 80°C for 30 minutes.
[0085] The mixed raw materials are added to a twin-screw extruder, the extrusion temperature is controlled at 180℃, the screw speed is 150r / min, and the extruded strips are then pelletized.
[0086] The granules are placed into an injection molding machine and molded using a honeycomb mesh mold at an injection temperature of 190℃ and a pressure of 120MPa to obtain honeycomb mesh reinforcing ribs.
[0087] Example 10
[0088] Preparation of biodegradable tourniquets:
[0089] Take the biodegradable tourniquet base layer prepared in Example 5 and place it on a flat and clean workbench.
[0090] Take the honeycomb mesh reinforcing strip prepared in Example 8 and place it on the upper surface of the biodegradable tourniquet base layer, ensuring accurate positioning.
[0091] The biodegradable tourniquet base layer with the honeycomb mesh reinforcing strips placed is transferred to a hot press laminating machine. The hot press temperature is set to 150℃, the pressure to 50MPa, and the hot press time to 2 minutes. The hot press laminating machine is started, allowing the honeycomb mesh reinforcing strips to embed into the biodegradable tourniquet base layer, resulting in a biodegradable tourniquet with honeycomb mesh reinforcing strips.
[0092] Example 11
[0093] Preparation of biodegradable tourniquets:
[0094] Take the biodegradable tourniquet base layer prepared in Example 6 and place it on a flat and clean workbench.
[0095] Take the honeycomb mesh reinforcing strip prepared in Example 8 and place it on the upper surface of the biodegradable tourniquet base layer, ensuring accurate positioning.
[0096] The biodegradable tourniquet base layer with the honeycomb mesh reinforcing strips placed is transferred to a hot press laminating machine. The hot press temperature is set to 160℃, the pressure to 60MPa, and the hot press time to 3 minutes. The hot press laminating machine is started, allowing the honeycomb mesh reinforcing strips to embed into the biodegradable tourniquet base layer, resulting in a biodegradable tourniquet with honeycomb mesh reinforcing strips.
[0097] Example 12
[0098] Preparation of biodegradable tourniquets:
[0099] Take the biodegradable tourniquet base layer prepared in Example 7 and place it on a flat and clean workbench.
[0100] Take the honeycomb mesh reinforcing strip prepared in Example 8 and place it on the upper surface of the biodegradable tourniquet base layer, ensuring accurate positioning.
[0101] The biodegradable tourniquet base layer with honeycomb mesh reinforcing strips placed is transferred to a hot press laminating machine. The hot press temperature is set to 170℃, the pressure to 80MPa, and the hot press time to 5 minutes. The hot press laminating machine is started, allowing the honeycomb mesh reinforcing strips to embed into the biodegradable tourniquet base layer, resulting in a biodegradable tourniquet with honeycomb mesh reinforcing strips.
[0102] Example 13
[0103] Preparation of biodegradable tourniquets:
[0104] Take the biodegradable tourniquet base layer prepared in Example 5 and place it on a flat and clean workbench.
[0105] Take the honeycomb mesh reinforcing strip prepared in Example 9 and place it on the upper surface of the biodegradable tourniquet base layer, ensuring accurate positioning.
[0106] The biodegradable tourniquet base layer with honeycomb mesh reinforcing strips placed is transferred to a hot press laminating machine. The hot press temperature is set to 155℃, the pressure to 55MPa, and the hot press time to 2.5 minutes. The hot press laminating machine is started, allowing the honeycomb mesh reinforcing strips to embed into the biodegradable tourniquet base layer, resulting in a biodegradable tourniquet with honeycomb mesh reinforcing strips.
[0107] Example 14
[0108] Preparation of biodegradable tourniquets:
[0109] Take the biodegradable tourniquet base layer prepared in Example 6 and place it on a flat and clean workbench.
[0110] Take the honeycomb mesh reinforcing strip prepared in Example 9 and place it on the upper surface of the biodegradable tourniquet base layer, ensuring accurate positioning.
[0111] The biodegradable tourniquet base layer with the honeycomb mesh reinforcing strips placed is transferred to a hot press laminating machine. The hot pressing temperature is set to 165℃, the pressure to 65MPa, and the hot pressing time to 3.5 minutes. The hot press laminating machine is started, allowing the honeycomb mesh reinforcing strips to embed into the biodegradable tourniquet base layer, resulting in a biodegradable tourniquet with honeycomb mesh reinforcing strips.
[0112] Example 15
[0113] Preparation of biodegradable tourniquets:
[0114] Take the biodegradable tourniquet base layer prepared in Example 7 and place it on a flat and clean workbench.
[0115] Take the honeycomb mesh reinforcing strip prepared in Example 9 and place it on the upper surface of the biodegradable tourniquet base layer, ensuring accurate positioning.
[0116] The biodegradable tourniquet base layer with honeycomb mesh reinforcing strips placed is transferred to a hot press laminating machine. The hot press temperature is set to 170℃, the pressure to 80MPa, and the hot press time to 4 minutes. The hot press laminating machine is started, allowing the honeycomb mesh reinforcing strips to embed into the biodegradable tourniquet base layer, resulting in a biodegradable tourniquet with honeycomb mesh reinforcing strips.
[0117] Example 16
[0118] Preparation of biodegradable tourniquets:
[0119] Take the biodegradable tourniquet base layer prepared in Example 5 and place it on a flat and clean workbench.
[0120] Take a honeycomb mesh reinforcing strip made of SEBS material and place it on the upper surface of the biodegradable tourniquet base layer, ensuring accurate positioning.
[0121] The biodegradable tourniquet base layer with the honeycomb mesh reinforcing strips placed is transferred to a hot press laminating machine. The hot press temperature is set to 150℃, the pressure to 50MPa, and the hot press time to 2 minutes. The hot press laminating machine is started, allowing the honeycomb mesh reinforcing strips to embed into the biodegradable tourniquet base layer, resulting in a biodegradable tourniquet with honeycomb mesh reinforcing strips.
[0122] Example 17
[0123] Preparation of biodegradable tourniquets:
[0124] Take the biodegradable tourniquet base layer prepared in Example 6 and place it on a flat and clean workbench.
[0125] Take a honeycomb mesh reinforcing strip made of SEBS material and place it on the upper surface of the biodegradable tourniquet base layer, ensuring accurate positioning.
[0126] The biodegradable tourniquet base layer with the honeycomb mesh reinforcing strips placed is transferred to a hot press laminating machine. The hot press temperature is set to 160℃, the pressure to 60MPa, and the hot press time to 3 minutes. The hot press laminating machine is started, allowing the honeycomb mesh reinforcing strips to embed into the biodegradable tourniquet base layer, resulting in a biodegradable tourniquet with honeycomb mesh reinforcing strips.
[0127] Example 18
[0128] Take the biodegradable tourniquet base layer prepared in Example 7 and place it on a flat and clean workbench.
[0129] Take a honeycomb mesh reinforcing strip made of SEBS material and place it on the upper surface of the biodegradable tourniquet base layer, ensuring accurate positioning.
[0130] The biodegradable tourniquet base layer with honeycomb mesh reinforcing strips placed is transferred to a hot press laminating machine. The hot press temperature is set to 170℃, the pressure to 80MPa, and the hot press time to 5 minutes. The hot press laminating machine is started, allowing the honeycomb mesh reinforcing strips to embed into the biodegradable tourniquet base layer, resulting in a biodegradable tourniquet with honeycomb mesh reinforcing strips.
[0131] Comparative Example 1
[0132] Preparation of tourniquet: Compared with Example 5, the accelerator in the raw materials was removed, and the rest were the same.
[0133] Comparative Example 2
[0134] Preparation of tourniquet: Compared with Example 5, the accelerator is replaced with the accelerator prepared in the following steps, and the rest are the same:
[0135] 70g of the biodegradable epoxy resin prepared in Example 1 and 1.2g of epoxy silane coupling agent were mixed at 130°C for 15 minutes and then extruded to granulate to obtain the accelerator.
[0136] The tourniquets obtained in Examples 5-7, 10-18 and Comparative Examples 1-2 were made into samples and subjected to the following physical property tests and degradation tests. The test results are shown in Table 1.
[0137] The degradation test involved cutting the tourniquets obtained in Examples 5-7, 10-18 and Comparative Examples 1-2 into granules, soaking them in DMF and nitric acid (the hydrogen ion concentration of the solution was calculated as 1M), and maintaining them at 85±5℃ for 2 hours. After that, they were taken out, washed with water and ethanol, dried, and then subjected to a photodegradation test (after 240 hours of ultraviolet irradiation at 290-400 nm, they were washed with water and ethanol, dried, weighed, and the degradation rate was calculated).
[0138] Among them, the tensile test: take 10cm of the tourniquet obtained by Examples 5-7, 10-18 and Comparative Examples 1-2, stretch it to twice the original length for half a minute, repeat three times, and finally wait 3 minutes to measure its rebound length.
[0139] Table 1
[0140]
[0141] As can be seen from the data in Table 1, the tourniquet granules obtained in Examples 10-18 have good elasticity, resilience and biodegradability.
[0142] Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. A biodegradable tourniquet with a reinforced structure, characterized in that, include: A base layer and a reinforcing rib layer; the reinforcing rib layer is disposed on the outer side of the base layer; The base layer comprises the following raw materials in parts by weight: 50-80 parts polyethylene and 20-50 parts accelerator; The accelerator is obtained by mixing and granulating biodegradable epoxy resin, epoxy silane coupling agent and nano titanium dioxide. The reinforcing rib layer includes several reinforcing ribs disposed on the base layer; The biodegradable epoxy resin is prepared by hyperbranching and epoxidative end-capping of biodegradable triol and 1,6-adipic acid. The hyperbranching reaction conditions are as follows: under the action of the first organic solvent and the esterification reaction catalyst, the temperature is 90-150℃, the time is 4-8h, and the molar ratio of degradable triol to 1,6-adipic acid is 2-3:
3. The epoxidation end-capping reaction is a reaction between the hyperbranching reaction product and epichlorohydrin; The epoxidation end-capping reaction includes: The hyperbranched reaction product and epichlorohydrin were heated to reflux for 4-8 hours. Then, a second organic solvent and NaOH were added, and the mixture was heated to 50-55°C and stirred for 4-8 hours. The reaction was then stopped, and the product was post-treated to obtain a biodegradable epoxy resin. The biodegradable triol is made from p-hydroxyaniline and formaldehyde; The molar ratio of p-hydroxyaniline to formaldehyde is 1:3-3.2; The reaction conditions for p-hydroxyaniline and formaldehyde are as follows: in a third organic solvent, at a temperature of 50-70°C, for a reaction time of 5-8 hours.
2. The biodegradable tourniquet with a reinforced structure according to claim 1, characterized in that, The reinforcing ribs of the reinforcing rib layer are mesh-like, diagonal-patterned, or honeycomb-like.
3. The biodegradable tourniquet with a reinforced structure according to claim 1, characterized in that, The mass ratio of the biodegradable epoxy resin, epoxy silane coupling agent, and nano titanium dioxide is 55-70:1.2-3:30-45, the mixing temperature is 50-70℃, and the mixing time is 10-30 min.
4. A biodegradable tourniquet with a reinforced structure according to claim 1, characterized in that, The reinforcing ribs comprise the following raw materials in parts by weight: 55-65 parts polylactic acid, 25-35 parts polycaprolactone, 5-10 parts nano-hydroxyapatite, 8-12 parts polyethylene glycol (Mw=4000-6000), and 3-5 parts triethyl citrate.
5. A biodegradable tourniquet with a reinforced structure according to claim 1, characterized in that, The reinforcing ribs are made of SEBS material.
6. The method for preparing a biodegradable tourniquet with a reinforced structure according to claim 1, characterized in that, include: After the polyethylene and accelerator are melt-mixed, they are extruded and molded to obtain the base layer of the biodegradable tourniquet; The reinforcing ribs are placed on the outside of the base layer of the biodegradable tourniquet and then laminated using a hot press laminating machine to obtain a biodegradable tourniquet with a reinforcing rib layer.
Citation Information
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Degradable hyperbranched epoxy resin and preparation method thereof
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