Fluorescent visual transparent polyvinylidene fluoride surgical suture, preparation method and application

Abstract

The application discloses a kind of fluorescent visual transparent polyvinylidene fluoride surgical suture, preparation method and application, belong to medical fiber technical field, including the following steps: with fluorescein O-acrylate, methyl methacrylate, N,N'- methylene bisacrylamide are added in deionized water and anhydrous ethanol mixed solution with mass fraction ratio, it is mixed evenly, then initiator is added, obtain fluorescent functional nanometer microspheres;With the nanometer microspheres of fluorescent function and polyvinylidene fluoride resin are blended after being sent into extruder one, polyvinylidene fluoride resin is added into single screw extruder two, it is sent to composite spinning assembly, after being shaped by composite spinneret, after water cooling, stretching, heat setting, obtain fluorescent visual transparent polyvinylidene fluoride surgical suture;The application has high strength, transparent characteristics, and can effectively indicate the position of surgical suture, solve the problem that transparent polyvinylidene fluoride surgical suture is difficult to see in operation process, improve surgical suturing efficiency, reduce the risk of suturing.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of medical fibers, in particular to a fluorescent visual transparent polyvinylidene fluoride surgical suture, a preparation method and application. BACKGROUND

[0002] Surgical sutures are widely used in surgical operations or trauma treatment for suture and hemostasis. Surgical sutures include absorbable sutures and non-absorbable sutures. In addition, with the development of medicine and material science, different functional sutures have appeared. Among them, transparent surgical sutures are mainly made of polypropylene, polyester, polyvinylidene fluoride, nylon and other high molecular materials. Because the color of transparent surgical suture is similar to the skin, it is more concealed after suture, which helps to reduce the obviousness of scar, and is especially suitable for suture of face and other exposed parts. At the same time, the surface of transparent suture is smooth, and it is not easy to adsorb bacteria, so it can reduce the risk of infection. Some sutures may also be treated specially, such as coating or antibacterial treatment, to further enhance their anti-infection ability. In addition, the compatibility of transparent surgical suture with human tissue is good, which helps to reduce the inflammatory reaction and promote wound healing.

[0003] However, because the color of transparent surgical suture is similar to the skin and tissue, it may be difficult for doctors to clearly see the position and direction of the line during the operation, which increases the difficulty of operation. In order to ensure the accuracy and effectiveness of suture, doctors need to have higher operation skills and judgment to overcome the visual obstruction of transparent line. By adding a small amount of fluorescent agent in the surgical suture, the surgical suture can remain transparent while emitting light under special light sources such as ultraviolet light to indicate the surgical suture. However, fluorescent agents are small molecules, which may cause migration and precipitation in polymers, which may cause secondary infection of wounds or tissues SUMMARY

[0004] The present application aims at the deficiencies of the prior art, and provides a fluorescent visual transparent polyvinylidene fluoride surgical suture, a preparation method and application. In the process of preparing the suture, only a small amount of fluorescent functional nanospheres are added, which does not affect the transparent appearance of the polyvinylidene fluoride surgical suture, and the surgical suture emits light under ultraviolet light, which can effectively indicate the position of the surgical suture, solve the problem that the transparent polyvinylidene fluoride surgical suture is difficult to see during the operation, improve the surgical suture efficiency and reduce the suture risk.

[0005] Technical scheme: The preparation method of the fluorescent visual transparent polyvinylidene fluoride surgical suture provided by the present application comprises the following steps:

[0006] Step 1, preparing nanospheres with fluorescent function

[0007] 1.1, adding fluorescein O-acrylate, methyl methacrylate, N, N'- methylene bisacrylamide in a mass ratio of (10-20):(78.5-88.5):1.5 into a mixed solution composed of deionized water and anhydrous ethanol;

[0008] 1.2, after mixing evenly, adding an initiator, the reaction system is protected by nitrogen, and the reaction is carried out at 75 o C for 8 hours, then centrifuging, washing with water for 3 times, and drying at 60 C for 24 hours to obtain fluorescent functional nanomicrospheres;

[0009] Step 2, preparing a blend

[0010] 2.1, weighing the fluorescent functional nanomicrospheres and the polyvinylidene fluoride resin according to the proportion, and adding them into a banbury mixer;

[0011] 2.2, banburying at 190 C for 10 minutes, the banburying speed is 50 rpm / min, and the blend is obtained by discharging and pelletizing; the mass ratio of the fluorescent functional nanomicrospheres and the polyvinylidene fluoride resin ranges from (0.05-0.2):(99.8-99.95);

[0012] Step 3, preparing a fluorescently visible polyvinylidene fluoride surgical suture

[0013] 3.1, adding the blend prepared in step 2 into single screw extruder one, sending it to the core layer flow channel of a composite spinning assembly, adding the polyvinylidene fluoride resin into single screw extruder two, sending it to the skin layer flow channel of the composite spinning assembly, and setting the temperature of the third segment of the extruder to 220 C / 230 C / 240 C; the temperature is the set temperature of the third segment of the extruder, and the molten polymer directly passes through the extruder pipe without staying.

[0014] 3.2, after forming through a composite spinneret, water cooling, stretching, and heat setting, the fluorescently visible transparent polyvinylidene fluoride surgical suture with a core layer and a skin layer is obtained.

[0015] Further, the volume ratio of the deionized water and the anhydrous ethanol in step 1.1 is 1:3, the mass ratio of the total mass of the fluorescein O-acrylate, the methyl methacrylate, and the N, N'-methylene bisacrylamide to the mass of the mixed solution is 1:25, the initiator is ammonium persulfate, and the mass of the initiator is 3% of the total mass of the fluorescein O-acrylate, the methyl methacrylate, and the N, N'-methylene bisacrylamide.

[0016] Further, the spinneret hole diameter of the composite spinneret in step 3.2 in step 3.2 is 0.12-0.24mm, the water cooling temperature is 35℃, the water bath length is 2 meters, and the drawing process is two-stage drawing, wherein the first-stage drawing temperature is 85℃, and the drawing ratio is 4 times; the second-stage drawing temperature is 140℃, and the drawing ratio is 1.2 times.

[0017] Further, the temperature of heat setting in step 3.2 is 150℃.

[0018] Further, the structure of the fluorescein O-acrylate in step 1.1 is as follows:

[0019] .

[0020] Further, the diameter of the fluorescently visible polyvinylidene fluoride surgical suture prepared in step 3 ranges from 0.05 to 0.1mm, and the average diameter of the fluorescent functional nanomicrospheres prepared in step 1 is 260nm.

[0021] A fluorescently visible transparent polyvinylidene fluoride surgical suture is obtained by the above preparation method.

[0022] The application of a fluorescently visible transparent polyvinylidene fluoride surgical suture in biomedical science.

[0023] The application of the above suture in biomedical science for non-therapeutic purposes.

[0024] Advantages: Compared with the prior art, the advantages of the present application are:

[0025] (1) The present application polymerizes fluorescein O-acrylate, N,N'-methylene bisacrylamide and methyl methacrylate to obtain fluorescent functional nanomicrospheres, and only water, alcohol and monomers are used in the synthesis process without other additives, which ensures the cleanliness during synthesis. The average size of the microspheres is 260nm. On the one hand, at a lower content, the suture can have a transparent appearance and mechanical strength without affecting the original application scenario of the surgical suture; on the other hand, since the fluorescein O-acrylate is polymerized into a macromolecule, there is no problem of migration and precipitation, thereby ensuring the biological safety of the surgical suture. At the same time, the fluorescent microspheres emit light under ultraviolet lamp irradiation, which can clearly indicate the position of the surgical suture, facilitating the operation of the doctor and ensuring the accuracy and effectiveness of the suture.

[0026] (2) The present application uses a composite molding method to prepare a fluorescently visible transparent polyvinylidene fluoride surgical suture, and the outer layer is pure polyvinylidene fluoride resin, which further avoids the risk of biological compatibility and biological toxicity caused by the addition of fluorescent functional nanomicrospheres. At the same time, the surface properties of the polyvinylidene fluoride resin are retained, and the original functions of the surgical suture such as lubricity and biocompatibility are maintained. Attached Figure Description

[0027] Figure 1 This is a transmission electron microscope image of the nanoparticles in this invention;

[0028] Figure 2 This is a distribution diagram of nanoparticles in the resin in this invention;

[0029] Figure 3 This is the suture without added nanoparticles in this invention;

[0030] Figure 4 It is the fluorescent suture prepared in this invention;

[0031] Figure 5 This is a longitudinal section of the fluorescent suture prepared according to the present invention;

[0032] Figure 6 This is the cross-section of the fluorescent suture prepared in this invention. Detailed Implementation

[0033] The technical solution of the present invention will be described in detail below with reference to the accompanying drawings, but the scope of protection of the present invention is not limited to the embodiments described.

[0034] Example 1:

[0035] Step 1: Preparation of fluorescent functional nanospheres

[0036] 10 g of fluorescein O-acrylate, 88.5 g of methyl methacrylate, and 1.5 g of N,N′-methylenebisacrylamide were added to a mixed solution of 625 mL of deionized water and 1875 mL of anhydrous ethanol and mixed thoroughly. 3 g of ammonium persulfate was dissolved in 10 g of water and then added to the reaction system. The reaction system was protected under nitrogen atmosphere and the mixture was kept at 75 °C. o After reacting at C for 8 hours, the mixture was centrifuged, washed three times with water, and dried to obtain fluorescent functional nanospheres with an average diameter of 260 nm.

[0037] Step 2: Preparation of blends

[0038] Weigh 10 g of fluorescent functional nanospheres and 4990 g of polyvinylidene fluoride resin, add them to a mixer, and mix at 190 °C for 10 minutes at a speed of 50 rpm / min. After discharging and pelletizing, the blend is obtained.

[0039] Step 3: Preparation of fluorescent, transparent polyvinylidene fluoride surgical sutures

[0040] 7 parts of the blend was fed into single screw extruder 1 to the core layer of the composite spinning assembly, 3 parts of polyvinylidene fluoride resin was fed into single screw extruder 2 to the skin layer of the composite spinning assembly, the extrusion temperature was 220℃ / 230℃ / 240℃, after forming through the composite spinneret with a spinneret diameter of 0.12 mm, water cooling, stretching, heat setting, the fluorescent visual transparent polyvinylidene fluoride surgical suture with a diameter of 0.05 mm was obtained. The water cooling temperature was 35℃, the water bath length was 2 meters, the stretching process was two-stage stretching, wherein the first-stage stretching temperature was 85℃, the stretching ratio was 3.8 times; the second-stage stretching temperature was the stretching temperature of 140℃, the stretching ratio was 1.2 times. The heat setting temperature was 150℃. The surgical suture was transparent, the mechanical strength was 5.9 cN / dtex, and had good luminescence effect under the ultraviolet lamp, which was clearly visible to the naked eye.

[0041] In this embodiment, the diameter of the surgical suture was 0.05 mm, and the average diameter of the fluorescent functional nanometer microspheres was 260 nm.

[0042] Example 2

[0043] Step 1: Preparation of fluorescent functional nanometer microspheres

[0044] 20 g of fluorescein O-acrylate, 78.5 g of methyl methacrylate, 1.5 g of N,N'-methylenebisacrylamide were added into a mixed solution of 625 mL of deionized water and 1875 mL of anhydrous ethanol, and 3 g of ammonium persulfate was added after uniform mixing, and the reaction system was protected by nitrogen. After 75 o C reaction for 8 hours, followed by centrifugation, water washing for 3 times, and drying, the fluorescent functional nanometer microspheres with an average diameter of 260 nm were obtained.

[0045] Step 2: Preparation of the blend

[0046] 2.5 g of the fluorescent functional nanometer microspheres and 4997.5 g of polyvinylidene fluoride resin were weighed and added into the internal mixer, and the internal mixing was carried out at 190℃ for 10 minutes, the rotation speed of the internal mixer was 50 rpm / min, and the blend was obtained through discharge and pelletizing.

[0047] Step 3: Preparation of the fluorescent visual transparent polyvinylidene fluoride surgical suture

[0048] Put 5 parts of the blend into single screw extruder 1, send to the core layer of the composite spinning assembly, put 5 parts of polyvinylidene fluoride resin into single screw extruder 2, send to the skin layer of the composite spinning assembly, the extrusion temperature is 220℃ / 230℃ / 240℃, after forming through the composite spinneret with a spinneret diameter of 0.12 mm, cooling, stretching, heat setting to obtain the fluorescent visual transparent polyvinylidene fluoride surgical suture with a diameter of 0.05 mm. The stretching process is two-stage stretching, wherein the first-stage stretching temperature is 85℃, and the stretching ratio is 3.8 times; the second-stage stretching temperature is the stretching temperature of 140℃, and the stretching ratio is 1.2 times. The heat setting temperature is 150℃.

[0049] The surgical suture is transparent, the mechanical strength is 5.7 cN / dtex, and has good light emitting effect under the ultraviolet lamp, which is clearly visible to the naked eye.

[0050] Example 3

[0051] Step 1: Preparation of fluorescent functional nanospheres

[0052] Put 15 g of fluorescein O-acrylate, 85 g of methyl methacrylate, 1.5 g of N,N'-methylenebisacrylamide into a mixed solution of 625 mL of deionized water and 1875 mL of anhydrous ethanol, mix uniformly, then add 3 g of ammonium persulfate, protect the reaction system with nitrogen, and react at 75 o C for 8 hours, then centrifuge, wash with water for 3 times, and dry to obtain fluorescent functional nanospheres with an average diameter of 260 nm.

[0053] Step 2: Preparation of the blend

[0054] Weigh 5 g of fluorescent functional nanospheres and 4995 g of polyvinylidene fluoride resin, put them into an internal mixer, mix at 190℃ for 10 minutes, the rotation speed of the internal mixer is 50 rpm / min, and then discharge and granulate to obtain the blend.

[0055] Step 3: Preparation of fluorescent visual transparent polyvinylidene fluoride surgical suture

[0056] Put 6 parts of the blend into single screw extruder 1, send to the core layer of the composite spinning assembly, put 4 parts of polyvinylidene fluoride resin into single screw extruder 2, send to the skin layer of the composite spinning assembly, the extrusion temperature is 220℃ / 230℃ / 240℃, after forming through the composite spinneret with a spinneret diameter of 0.24 mm, cooling, stretching, heat setting to obtain the fluorescent visual transparent polyvinylidene fluoride surgical suture with a diameter of 0.1 mm. The stretching process is two-stage stretching, wherein the first-stage stretching temperature is 85℃, and the stretching ratio is 3.8 times; the second-stage stretching temperature is the stretching temperature of 140℃, and the stretching ratio is 1.2 times. The heat setting temperature is 150℃.

[0057] The surgical suture is transparent, has a mechanical strength of 5.4 cN / dtex, and has a good light-emitting effect under an ultraviolet lamp, which is clearly visible to the naked eye.

[0058] Comparative Example 1

[0059] The difference from Example 1 is that 15 g of fluorescent functional nanomicrospheres and 4985 g of polyvinylidene fluoride resin are weighed in step 2, so that the mass percentage content of fluorescent functional nanomicrospheres in the blend reaches 0.3%. The results show that the surgical suture has a white core and is visually opaque, with a mechanical strength of 5.6 cN / dtex.

[0060] Comparative Example 2

[0061] The difference from Example 1 is that 2 g of fluorescent functional nanomicrospheres and 4998 g of polyvinylidene fluoride resin are weighed in step 2, so that the mass percentage content of fluorescent functional nanomicrospheres in the blend reaches 0.04%.

[0062] The surgical suture is transparent, but the light-emitting effect under an ultraviolet lamp is not significant, and it is difficult to identify with the naked eye, with a mechanical strength of 5.7 cN / dtex.

[0063] Experimental Example 1

[0064] According to the non-absorbable surgical suture industry standard YY / T0167-2020, the suture prepared in Examples 1-3 was tested for wire diameter mm, knot breaking force N, elongation %, strength N, and strength cN / dtex, and the results are shown in the following table.

[0065] The results of Example 1 are as follows:

[0066]

[0067] The results of Example 2 are as follows:

[0068]

[0069] The results of Example 3 are as follows:

[0070]

[0071] As described above, although the present application has been represented and described with reference to specific preferred embodiments, it is not to be construed as being limited thereto. Various changes in form and details can be made thereto without departing from the spirit and scope of the application as defined in the appended claims.

Claims

1. A method for preparing a fluorescent visual transparent polyvinylidene fluoride surgical suture, characterized by comprising the following steps: Step 1, preparing nano microspheres with fluorescent function 1.1, the fluorescein O-acrylate, methyl methacrylate, N, N'- methylene double acrylamide is added to the mixed solution composed of deionized water and anhydrous ethanol in the mass ratio of (10-20): (78.5-88.5): 1.5; 1.2 After the mixture is homogeneous, add the initiator. Purge the reaction system with nitrogen and maintain the temperature at 75°C. o The reaction was carried out at C for 8 hours, followed by centrifugation, washing with water 3 times, and drying at 60℃ for 24 hours to obtain fluorescent functional nanospheres. Step 2, preparation of the blend 2.1, the mass ratio of the nano microspheres with fluorescence function and the polyvinylidene fluoride resin is (0.05~0.2):(99.8~99.95), and the polyvinylidene fluoride resin is added to the internal mixer; 2.2, the internal mixer is mixed at 190 ℃ for 10 minutes, and the rotation speed of the internal mixer is 50 rpm / min; the blend is obtained by discharging and pelletizing; the mass ratio of the nano microspheres with fluorescence function and the polyvinylidene fluoride resin is (0.05~0.2):(99.8~99.95); Step 3, preparation of the fluorescent visible transparent polyvinylidene fluoride surgical suture 3.1, the blend prepared in step 2 is added to single screw extruder one, and sent to the core layer flow channel of the composite spinning assembly; the polyvinylidene fluoride resin is added to single screw extruder two, and sent to the skin layer flow channel of the composite spinning assembly; the three-stage temperature of the extruder is 220℃ / 230℃ / 240℃; 3.2, after forming through the composite spinneret, water cooling, stretching and heat setting, the fluorescent visible transparent polyvinylidene fluoride surgical suture with core layer and skin layer is obtained.

2. The preparation method of the fluorescent visible transparent polyvinylidene fluoride surgical suture according to claim 1, wherein the volume ratio of the deionized water and the anhydrous ethanol in step 1.1 is 1:3, the total mass of the fluorescein O-acrylate, methyl methacrylate and N, N'- methylene double acrylamide is 1:25 of the mass of the mixed solution, the initiator is ammonium persulfate, and the mass of the initiator is 3% of the total mass of the fluorescein O-acrylate, methyl methacrylate and N, N'- methylene double acrylamide.

3. The process for preparing a fluorescently visible transparent polyvinylidene fluoride surgical suture according to claim 1, characterized in that: The spinneret hole diameter of the composite spinneret in step 3.2 is 0.12-0.24mm, the water cooling temperature is 35℃, the water bath length is 2 meters, and the stretching process is two-stage stretching, wherein the first-stage stretching temperature is 85 ℃, and the stretching ratio is 4 times; the second-stage stretching temperature is 140 ℃, and the stretching ratio is 1.2 times.

4. The process for preparing a fluorescently visible transparent polyvinylidene fluoride surgical suture according to claim 1, characterized in that: The heat setting temperature in step 3.2 is 150℃.

5. The process for preparing a fluorescently visible transparent polyvinylidene fluoride surgical suture according to claim 1, characterized in that: The structural formula of the fluorescein O-acrylate in step 1.1 is as follows: 。 6. The process for preparing a fluorescently visible transparent polyvinylidene fluoride surgical suture according to claim 1, characterized in that: The diameter of the fluorescent visible polyvinylidene fluoride surgical suture prepared in step 3 is 0.05-0.1mm, and the average diameter of the fluorescent functional nano microspheres prepared in step 1 is 260 nm.

7. A fluorescently visualized transparent polyvinylidene fluoride surgical suture, characterized by: Obtained by the preparation method of any one of claims 1~5.

Images