Degradable tourniquet and method of making same

Abstract

The application relates to a degradable tourniquet and a preparation method thereof, and belongs to the technical field of tourniquet preparation. The tourniquet comprises the following raw materials in parts by weight: 50-80 parts of polyethylene, and 20-50 parts of a promoter; the promoter is obtained by mixing, granulating degradable epoxy resin, epoxy silane coupling agent and nano titanium dioxide. The application introduces the promoter into the polyethylene, the promoter is obtained by melt blending and extrusion granulation of the degradable epoxy resin and the nano titanium dioxide, the introduction of the promoter not only utilizes the photocatalytic degradation effect of the nano titanium dioxide on the polyethylene, but also utilizes the characteristics of the interpenetrating network formed under the toughening and self-curing effect of the degradable epoxy resin, so that the final obtained composite is endowed with good degradation performance and elastic performance.

Description

Technical Field

[0001] This invention belongs to the field of tourniquet preparation technology, and specifically relates to a biodegradable tourniquet 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 and its preparation method.

[0006] The first objective of this invention is achieved through the following technical solution:

[0007] A biodegradable tourniquet comprises the following raw materials in parts by weight: 50-80 parts polyethylene and 20-50 parts accelerator;

[0008] The accelerator is obtained by mixing and granulating biodegradable epoxy resin, epoxy silane coupling agent and nano titanium dioxide.

[0009] 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.

[0010] Furthermore, the biodegradable epoxy resin is prepared by hyperbranching and epoxidative end-capping of biodegradable triol and 1,6-adipic acid.

[0011] 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.

[0012] Preferably, to obtain hyperbranched reaction products with higher branching degree, the hyperbranching reaction includes:

[0013] 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.

[0014] Furthermore, the first organic solvent is one of N,N-dimethylformamide (DMF), benzene, and toluene.

[0015] Furthermore, the catalyst for the esterification reaction is one of concentrated sulfuric acid and p-toluenesulfonic acid.

[0016] Furthermore, the epoxidation end-capping reaction is a reaction between the hyperbranching reaction product and epichlorohydrin.

[0017] Furthermore, the epoxidation capping reaction includes:

[0018] 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.

[0019] Furthermore, the second organic solvent is one of chloroform, N,N-dimethylformamide (DMF), and toluene.

[0020] Furthermore, the biodegradable triol is made from p-hydroxyaniline and formaldehyde.

[0021] Furthermore, the molar ratio of p-hydroxyaniline to formaldehyde is 1:3-3.2.

[0022] Furthermore, the reaction conditions for p-hydroxyaniline and formaldehyde are: in a third organic solvent, at a temperature of 50-70°C, for a reaction time of 5-8 hours.

[0023] Furthermore, the third organic solvent is one of ethanol, chloroform, and N,N-dimethylformamide (DMF).

[0024] Preferably, the reaction for obtaining the degradable triol includes:

[0025] 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.

[0026] The molecular structure of the biodegradable triol is shown below.

[0027]

[0028] 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.

[0029] 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.

[0030] The second objective of this invention is achieved through the following technical solution:

[0031] A method for preparing a biodegradable tourniquet, comprising:

[0032] After the polyethylene and accelerator are melt-mixed, they are extruded and molded to obtain a biodegradable tourniquet.

[0033] The beneficial effects of this invention are:

[0034] The present invention provides a biodegradable tourniquet, which introduces an accelerator into polyethylene. 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 biodegradable epoxy resin to form an interpenetrating network, thus endowing the final composite with good degradation performance and elasticity.

[0035] 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.

[0036] 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.

[0037] 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. Detailed Implementation

[0038] 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.

[0039] Example 1

[0040] Preparation of biodegradable epoxy resin:

[0041] 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.

[0042] 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 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.

[0043] Example 2

[0044] Preparation of biodegradable epoxy resin:

[0045] A1. Mix 0.32 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 5-8 h, rotary evaporate, and purify by column chromatography to obtain degradable triol.

[0046] 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, take the organic layer, and dry to obtain the biodegradable epoxy resin.

[0047] Example 3

[0048] Preparation of accelerators:

[0049] 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.

[0050] Example 4

[0051] Preparation of accelerators:

[0052] 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.

[0053] Example 5

[0054] Preparation of biodegradable tourniquets:

[0055] 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. The melting and mixing temperature is 150-170°C and the extrusion temperature is 180-230°C.

[0056] Example 6

[0057] Preparation of biodegradable tourniquets:

[0058] After 65 parts by weight of polyethylene and 35 parts by weight of the accelerator prepared in Example 5 were melt-mixed, the mixture was extruded and molded to obtain a biodegradable tourniquet. The melt mixing temperature was 150-170°C and the extrusion temperature was 180-230°C.

[0059] Example 7

[0060] Preparation of biodegradable tourniquets:

[0061] After melting and mixing 50 parts by weight of polyethylene and 50 parts by weight of the accelerator prepared in Example 4, the mixture is extruded and molded to obtain a biodegradable tourniquet. The melting and mixing temperature is 150-170°C and the extrusion temperature is 180-230°C.

[0062] Comparative Example 1

[0063] Preparation of tourniquet: Compared with Example 5, the accelerator in the raw materials was removed, and the rest were the same.

[0064] Comparative Example 2

[0065] 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:

[0066] 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.

[0067] The tourniquets obtained in Examples 5-7 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.

[0068] The degradation test involved cutting the tourniquets obtained in Examples 5-7 and Comparative Examples 1-2 into granules, immersing them in DMF and nitric acid (with a hydrogen ion concentration of 1 M), and maintaining them at 85±5°C for 2 hours. Afterward, the granules were removed, washed with water and ethanol, dried, and then subjected to a photodegradation test (irradiated with 290-400 nm ultraviolet light for 240 hours, followed by washing with water and ethanol, drying, weighing, and calculating the degradation rate).

[0069] Table 1

[0070] Serial Number Tensile strength Elongation at break Degradation rate Test Standards GB / T 1040 GB / T 1040 / unit MPa ％ ％ Example 5 21.2 403 92.1 Example 6 23.6 435 92.5 Example 7 24.7 451 93.3 Comparative Example 1 18.5 356 13.8 Comparative Example 2 21.0 395 64.5

[0071] As can be seen from the data in Table 1, the tourniquet granules obtained in Examples 5-7 have good elasticity and biodegradability.

[0072] 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 degradable tourniquet, characterized in that, The composition comprises the following raw materials by weight: 50-80 parts of polyethylene, 20-50 parts of accelerator; The accelerator is obtained by mixing and granulating degradable epoxy resin, epoxy silane coupling agent and nano titanium dioxide; The degradable epoxy resin is made of degradable trihydric alcohol and 1,6-hexanedioic acid through hyperbranched reaction and epoxidation capping reaction; The hyperbranched reaction conditions are as follows: under the action of a first organic solvent and esterification reaction catalyst, the temperature is 90-150℃, the time is 4-8h, and the molar ratio of degradable trihydric alcohol to 1,6-hexanedioic acid is 2-3:3; The epoxidation capping reaction is the reaction of hyperbranched reaction product and epichlorohydrin; The degradable trihydric alcohol is made of p-hydroxyaniline and formaldehyde; The molar ratio of p-hydroxyaniline to formaldehyde is 1:3-3.2; The molecular structure of the degradable trihydric alcohol is as follows: 。 2. The degradable tourniquet of claim 1, wherein, The mass ratio of the degradable 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 10-30min.

3. The degradable tourniquet of claim 1, wherein, The epoxidation capping reaction comprises: The hyperbranched reaction product and epichlorohydrin are heated to reflux, refluxed for 4-8h, then a second organic solvent and NaOH are added, heated to 50-55℃, and kept stirring for 4-8h, then the reaction is stopped, and the degradable epoxy resin is obtained after post-treatment.

4. The degradable tourniquet of claim 1, wherein, The reaction conditions of p-hydroxyaniline and formaldehyde are as follows: in a third organic solvent, the temperature is 50-70℃, and the reaction time is 5-8h.

5. The method of claim 1, wherein the degradable tourniquet is prepared by the steps of: The composition comprises: After the polyethylene and the accelerator are melt-mixed, they are extruded and molded to obtain the degradable tourniquet.

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