Degradable tourniquet and preparation method thereof

Abstract

The invention 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 an accelerant, the accelerant is obtained by mixing and granulating degradable epoxy resin, an epoxy silane coupling agent and nano titanium dioxide. According to the invention, the accelerant is introduced into the polyethylene, and the accelerant is prepared from degradable epoxy resin and nano titanium dioxide through melt blending and extrusion granulation, so that the photocatalytic degradation effect of the nano titanium dioxide on the polyethylene is utilized; and the characteristic that the degradable epoxy resin forms an interpenetrating network under the toughening and self-curing effects is utilized, so that the finally obtained compound is endowed with good degradation performance and elastic performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of the preparation of tourniquets, and particularly relates to a degradable tourniquet and a preparation method thereof. Background Art

[0002] The tourniquet is made of medical polymer materials, is long and flat, and has strong stretchability. It is suitable for one-time use in medical institutions during routine treatment and rescue for infusion, blood drawing, blood transfusion, and hemostasis; or for emergency hemostasis in case of limb bleeding or bleeding caused by snake and insect bites in the wild.

[0003] The common tourniquet in the existing market is a rubber tourniquet. With the abandonment of the rubber tourniquet, it becomes medical waste rubber, and rubber is difficult to degrade, ultimately causing problems in the treatment of medical waste rubber.

[0004] When using a degradable polymer as the raw material for the tourniquet, its elastic properties cannot meet the requirements of the high elasticity of the tourniquet. Therefore, how to make a degradable tourniquet and its preparation method is an urgent problem to be solved at present. Summary of the Invention

[0005] In view of the above problems, the present invention provides a degradable tourniquet and a preparation method thereof.

[0006] The first object of the present invention is achieved by the following technical solutions:

[0007] A degradable tourniquet, comprising the following raw materials in parts by weight: 50 - 80 parts of polyethylene, 20 - 50 parts of a promoter;

[0008] The promoter is obtained by mixing and granulating a degradable epoxy resin, an epoxy group silane coupling agent, and nano-titanium dioxide.

[0009] Further, the mass ratio of the degradable epoxy resin, the epoxy group silane coupling agent, and the nano-titanium dioxide is 55 - 70:1.2 - 3:30 - 45, the temperature of the mixing is 50 - 70 °C, and the mixing time is 10 - 30 min.

[0010] Further, the degradable epoxy resin is made from a degradable triol and 1,6-hexanedioic acid through a hyperbranched reaction and an epoxidation end-capping reaction.

[0011] Further, the conditions of the hyperbranched reaction: under the action of a first organic solvent and an esterification reaction catalyst, the temperature is 90 - 150 °C, the time is 4 - 8 h, and the molar ratio of the degradable triol to 1,6-hexanedioic acid is 2 - 3:3.

[0012] Preferably, in order to obtain a hyperbranched reaction product with a higher degree of branching, the hyperbranched reaction includes:

[0013] After mixing the biodegradable triol, 1,6 - hexanedioic acid and DMF uniformly, concentrated sulfuric acid is added dropwise with stirring. After complete addition, it is heated to 90 - 110 °C, and stirring is continued for 1 - 2 h. Then it is heated to 120 - 150 °C and stirring is continued for 2 - 3 h. The reaction is stopped, and after post - treatment, a hyperbranched reaction product is obtained.

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

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

[0016] Further, the epoxidation capping reaction is the reaction of the hyperbranched reaction product and epichlorohydrin.

[0017] Further, the epoxidation capping reaction includes:

[0018] The hyperbranched reaction product and epichlorohydrin are heated to reflux for 4 - 8 h, then a second organic solvent and NaOH are added, and it is heated to 50 - 55 °C and kept stirring for 4 - 8 h. The reaction is stopped and after post - treatment, a biodegradable epoxy resin is obtained.

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

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

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

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

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

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

[0025] An aqueous formaldehyde solution (mass fraction 37%), p - hydroxyaniline and a third organic solvent are mixed uniformly, then heated to 50 - 70 °C and kept stirring for 5 - 8 h, and rotary evaporation is carried out to obtain the biodegradable triol.

[0026] The molecular structural formula of the biodegradable triol is shown as follows.

[0027]

[0028] In the present invention, according to the processing performance or antioxidant performance of the tourniquet, processing aids (such as lubricants) and antioxidants are added to the raw materials of the tourniquet;

[0029] The processing aids and antioxidants are processing aids and antioxidants for resins in the technical field, and the present invention does not make special limitations.

[0030] The second object of the present invention is achieved by the following technical solutions:

[0031] A preparation method of a degradable tourniquet, comprising:

[0032] Melting and mixing polyethylene and a promoter, and then extruding and molding to obtain a degradable tourniquet.

[0033] Advantages of the present invention:

[0034] For a degradable tourniquet of the present invention, by introducing a promoter into polyethylene, the promoter is prepared by melt blending and extrusion granulation of a degradable epoxy resin and nano-titanium dioxide. The introduction of this promoter not only utilizes the photocatalytic degradation effect of nano-titanium dioxide on polyethylene, but also utilizes the toughening and self-curing effects of the degradable epoxy resin to form an interpenetrating network, endowing the finally obtained composite with good degradation performance and elastic properties;

[0035] Significantly: First, the degradable epoxy resin in the present invention is a degradable hyperbranched epoxy resin, and the hyperbranched structure provides a large loading space for nano-titanium dioxide;

[0036] Second, the degradable epoxy resin in the present invention contains a s-triazine ring and an ester group degradable structure. Among them, the ester group can be rapidly degraded by heating in an organic solvent, and the s-triazine ring can be rapidly degraded under the conditions of heating (80 - 100 °C) and / or a catalyst (acidic or basic) in an organic solvent (such as DMF).

[0037] Other features and advantages of the present invention will be described in the subsequent specification, and some of them will become obvious from the specification or be understood by implementing the present invention. Detailed embodiments

[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 part of the embodiments of the present invention, rather than all of them. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0039] Example 1

[0040] Preparation of Degradable Epoxy Resin:

[0041] A1. Mix an aqueous solution containing 0.3 mol of formaldehyde (mass fraction 37%), 0.1 mol of p-hydroxyaniline, and 150 mL of ethanol evenly, heat to reflux, and stir for 5 h. Then perform rotary evaporation and column purification to obtain a degradable triol.

[0042] A2. Mix 0.22 mol of the degradable triol, 0.3 mol of 1,6-hexanedioic acid, and 300 mL of DMF evenly. While stirring, add concentrated sulfuric acid (mass fraction 98%, and the added mass is 1.5% of the total mass of the degradable triol and 1,6-hexanedioic acid). After complete addition, heat to 110 °C and continuously stir for 1 h. Then raise the temperature to 140 °C and continuously stir for 2 h to stop the reaction. Perform rotary evaporation, water washing, and drying to obtain a hyperbranched reaction product. Heat the obtained hyperbranched reaction product and epichlorohydrin (in excess, the added amount in this example is 0.9 mol) to reflux for 4 h. Rotary evaporate to remove the excess epichlorohydrin, then add 300 mL of DMF and excess NaOH (the added amount in this example is 1 mol), heat to 50 °C, keep warm and stir for 4 h. Perform rotary evaporation, water washing, take the organic layer, and dry to obtain a degradable epoxy resin.

[0043] Example 2

[0044] Preparation of Degradable Epoxy Resin:

[0045] A1. Mix an aqueous solution containing 0.32 mol of formaldehyde (mass fraction 37%), 0.1 mol of p-hydroxyaniline, and 150 mL of ethanol evenly, heat to reflux, and stir for 5 - 8 h. Then perform rotary evaporation and column purification to obtain a degradable triol.

[0046] A2. Mix 0.3 mol of the degradable triol, 0.3 mol of 1,6-hexanedioic acid, and 300 mL of DMF evenly. While stirring, add concentrated sulfuric acid (mass fraction 98%, and the added mass is 1.5% of the total mass of the degradable triol and 1,6-hexanedioic acid). After complete addition, heat to 90 °C and continuously stir for 2 h. Then raise the temperature to 120 °C and continuously stir for 3 h to stop the reaction. Perform rotary evaporation, water washing, and drying to obtain a hyperbranched reaction product. Heat the obtained hyperbranched reaction product and epichlorohydrin (in excess, the added amount in this example is 0.9 mol) to reflux for 8 h. Rotary evaporate to remove the excess epichlorohydrin, then add 300 mL of DMF and excess NaOH (the added amount in this example is 1 mol), heat to 55 °C, keep warm and stir for 8 h. Perform rotary evaporation, water washing, take the organic layer, and dry to obtain a degradable epoxy resin.

[0047] Example 3

[0048] Preparation of Promoter:

[0049] Mix 70 g of the degradable epoxy resin prepared in Example 1, 1.2 g of an epoxy group-containing silane coupling agent, and 30 g of nano-titanium dioxide at 70 °C for 15 min, then extrude and pelletize to obtain a promoter.

[0050] Example 4

[0051] Preparation of the promoter:

[0052] Mix 55 g of the degradable epoxy resin prepared in Example 2, 3 g of an epoxy group-containing silane coupling agent, and 45 g of nano-titanium dioxide at 50 °C for 30 min, then extrude and pelletize to obtain a promoter.

[0053] Example 5

[0054] Preparation of the degradable tourniquet:

[0055] Melt and mix 80 parts by weight of polyethylene and 20 parts by weight of the promoter prepared in Example 4, then extrude and mold to obtain a degradable tourniquet. The melt mixing temperature is 150 - 170 °C, and the extrusion temperature is 180 - 230 °C.

[0056] Example 6

[0057] Preparation of the degradable tourniquet:

[0058] Melt and mix 65 parts by weight of polyethylene and 35 parts by weight of the promoter prepared in Example 5, then extrude and mold to obtain a degradable tourniquet. The melt mixing temperature is 150 - 170 °C, and the extrusion temperature is 180 - 230 °C.

[0059] Example 7

[0060] Preparation of the degradable tourniquet:

[0061] Melt and mix 50 parts by weight of polyethylene and 50 parts by weight of the promoter prepared in Example 4, then extrude and mold to obtain a degradable tourniquet. The melt mixing temperature is 150 - 170 °C, and the extrusion temperature is 180 - 230 °C.

[0062] Comparative Example 1

[0063] Preparation of the tourniquet: Compared with Example 5, delete the promoter in the raw materials, and the rest is the same.

[0064] Comparative Example 2

[0065] Preparation of the tourniquet: Compared with Example 5, replace the promoter with the promoter prepared in the following steps, and the rest is the same:

[0066] 70 g of the degradable epoxy resin prepared in Example 1 and 1.2 g of an epoxy group-containing silane coupling agent were mixed at 130 °C for 15 min and then extruded and pelletized to obtain a promoter.

[0067] The tourniquets obtained in Examples 5-7 and Comparative Examples 1-2 were made into specimens for the following physical property tests and degradation tests. The test results are shown in Table 1.

[0068] Among them, the degradation test: The tourniquets obtained in Examples 5-7 and Comparative Examples 1-2 were cut into pellets, soaked in DMF and nitric acid (the hydrogen ion concentration of the solution was calculated as 1 M), and kept at 85 ± 5 °C for 2 hours. Then, they were taken out, washed with water, washed with ethanol, dried, and then subjected to a photo-degradation test (after 240 h of ultraviolet irradiation at 290-400 nm, washed with water, washed with ethanol, dried, the weight was measured, and the degradation rate was calculated).

[0069] Table 1

[0070] Serial number Tensile strength Elongation at break Degradation rate Test standard 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] From the data in Table 1, it can be seen that the pellets of the tourniquets obtained in Examples 5-7 have good elastic properties and degradable properties.

[0072] Although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements 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, It includes the following raw materials in parts by weight: 50 - 80 parts of polyethylene and 20 - 50 parts of accelerator; The accelerator is obtained by mixing and granulating biodegradable epoxy resin, epoxy - based silane coupling agent and nano - titanium dioxide.

2. The biodegradable tourniquet according to claim 1, wherein, The mass ratio of the biodegradable epoxy resin, epoxy - based silane coupling agent and nano - titanium dioxide is 55 - 70:1.2 - 3:30 - 45. The temperature of the mixing is 50 - 70 °C and the mixing time is 10 - 30 min.

3. The biodegradable tourniquet according to claim 1, characterized in that, The biodegradable epoxy resin is made from biodegradable triol and 1,6 - hexanedioic acid through hyperbranched reaction and epoxy - capped reaction.

4. The biodegradable tourniquet according to claim 3, characterized in that, The conditions of the hyperbranched reaction: under the action of the first organic solvent and the esterification reaction catalyst, the temperature is 90 - 150 °C, the time is 4 - 8 h, and the molar ratio of the biodegradable triol to 1,6 - hexanedioic acid is 2 - 3:

3.

5. The biodegradable tourniquet according to claim 3, characterized in that, The epoxy - capped reaction is the reaction between the hyperbranched reaction product and epichlorohydrin.

6. The biodegradable tourniquet according to claim 5, characterized in that, The epoxy - capped reaction includes: Heating the hyperbranched reaction product and epichlorohydrin to reflux for 4 - 8 h, then adding the second organic solvent and NaOH, heating to 50 - 55 °C, keeping warm and stirring for 4 - 8 h, stopping the reaction, and performing post - treatment to obtain the biodegradable epoxy resin.

7. The biodegradable tourniquet according to claim 3, characterized in that, The biodegradable triol is made from p - hydroxyaniline and formaldehyde.

8. The biodegradable tourniquet according to claim 7, wherein The molar ratio of p - hydroxyaniline to formaldehyde is 1:3 - 3.

2.

9. The biodegradable tourniquet according to claim 7, characterized in that, The reaction conditions of p - hydroxyaniline and formaldehyde: in the third organic solvent, the temperature is 50 - 70 °C and the reaction time is 5 - 8 h.

10. The preparation method of a degradable tourniquet according to claim 1, characterized in that, It includes: Melting and mixing polyethylene and the accelerator, and then extruding and molding to obtain the biodegradable tourniquet.

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