Fluorescent visible transparent polyvinylidene fluoride surgical suture as well as preparation method and application thereof

Abstract

The invention discloses a fluorescent visible transparent polyvinylidene fluoride surgical suture and a preparation method and application thereof, and belongs to the technical field of medical fibers.The preparation method comprises the following steps that fluorescein O-acrylate, methyl methacrylate and N, N '-methylene bisacrylamide are added into a mixed solution of deionized water and absolute ethyl alcohol according to the mass part ratio and mixed to be uniform, and then the fluorescent visible transparent polyvinylidene fluoride surgical suture is obtained; then adding an initiator to obtain the fluorescent functional nano-microspheres; nano microspheres with a fluorescent function and polyvinylidene fluoride resin are blended and then fed into a first extruder, the polyvinylidene fluoride resin is added into a second single-screw extruder, the materials are jointly fed into a composite spinning assembly, and after the materials are formed through a composite spinneret plate, the fluorescent visible transparent polyvinylidene fluoride surgical suture is obtained through water cooling, stretching and heat setting. The transparent polyvinylidene fluoride surgical suture has the advantages of being high in strength and transparent, the position of the surgical suture can be effectively indicated, the problem that the transparent polyvinylidene fluoride surgical suture is ugly clear in the surgical process is solved, the surgical suture efficiency is improved, and the suture risk is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of medical fibers, and particularly relates to a fluorescent visible transparent polyvinylidene fluoride surgical suture, a preparation method and an application thereof. Background Art

[0002] Surgical sutures are widely used in surgical operations or trauma treatments for functions such as suturing and hemostasis. Surgical sutures include absorbable sutures and non-absorbable sutures. In addition, with the development of medicine and materials science, sutures with different functions have emerged. Among them, transparent surgical sutures are mainly prepared from high molecular materials such as polypropylene, polyester, polyvinylidene fluoride, nylon, etc. Since the color of the transparent surgical suture is similar to that of the skin, it is relatively inconspicuous after suturing, which helps to reduce the obviousness of scars and is particularly suitable for suturing of the face and other exposed parts. At the same time, the surface of the transparent suture is smooth and not easy to adsorb bacteria, so the risk of infection can be reduced. Some sutures may also be specially treated, such as coating or antibacterial treatment, to further enhance their anti-infection ability. In addition, the transparent surgical suture has good compatibility with human tissues, which helps to reduce the inflammatory reaction and promote wound healing.

[0003] However, since the color of the transparent surgical suture is similar to that of the skin and tissues, it may be difficult for doctors to clearly see the position and direction of the suture during the operation, which increases the difficulty of the operation. To ensure the accuracy and effectiveness of suturing, doctors need to have higher operating skills and judgment to overcome the visual obstacle brought by the transparent suture. By adding a small amount of fluorescent agent to the surgical suture, the surgical suture can emit light under special light sources such as ultraviolet lamps while remaining transparent, so as to indicate the surgical suture. However, the fluorescent agent is a small molecule and there is a problem of migration and precipitation in the polymer, which may cause secondary infection of the wound or tissue. Summary of the Invention

[0004] Object of the Invention: The object of the present invention is to provide a fluorescent visible transparent polyvinylidene fluoride surgical suture, a preparation method and an application thereof in view of the deficiencies of the prior art. During the preparation of the suture, only a small amount of fluorescent functional nanospheres are added, which not only does not affect the transparent appearance of the polyvinylidene fluoride surgical suture, but also the surgical suture emits light under ultraviolet light, which can effectively indicate the position of the surgical suture, solves the problem that it is difficult to see clearly the transparent polyvinylidene fluoride surgical suture during the operation, improves the surgical suture efficiency, and reduces the suture risk.

[0005] Technical Solution: The preparation method of a fluorescent visible transparent polyvinylidene fluoride surgical suture according to the present invention includes the following steps: Step 1, prepare nanospheres with fluorescent function 1.1. Add fluorescein O - acrylate, methyl methacrylate, and N,N′-methylenebisacrylamide into a mixed solution composed of deionized water and absolute ethanol according to the mass ratio of (10 - 20):(78.5 - 88.5):1.5; 1.2. After mixing evenly, add an initiator. Protect the reaction system with nitrogen. React at 75 o °C for 8 hours. Then, centrifuge and wash three times with water, and dry at 60 °C for 24 hours to obtain fluorescent functional nanospheres; Step 2. Prepare the blend 2.1. Weigh the fluorescent functional nanospheres and polyvinylidene fluoride resin according to the ratio and add them into a mixer; 2.2. Knead at 190 °C for 10 minutes, with the mixer speed at 50 rpm / min. After discharging and pelletizing, obtain the blend; the mass ratio range of the fluorescent functional nanospheres to polyvinylidene fluoride resin is (0.05~0.2):(99.8~99.95); Step 3. Prepare a fluorescently visible polyvinylidene fluoride surgical suture 3.1. Add the blend prepared in Step 2 into single - screw extruder 1 and send it to the core layer channel of the composite spinning component. Add polyvinylidene fluoride resin into single - screw extruder 2 and send it to the skin layer channel of the composite spinning component. The temperatures of the three sections of the extruder are 220 °C / 230 °C / 240 °C; this temperature is the set temperature of the three sections of the extruder, and the molten polymer directly passes through the extruder pipe without staying.

[0006] 3.2. After forming through a composite spinneret, cool with water, stretch, and heat - set to obtain a fluorescently visible transparent polyvinylidene fluoride surgical suture with a core layer and a skin layer.

[0007] Furthermore, in Step 1.1, the volume ratio of the deionized water to the absolute ethanol is 1:3, the mass ratio of the total mass of fluorescein O - acrylate, methyl methacrylate, and N,N′-methylenebisacrylamide 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 fluorescein O - acrylate, methyl methacrylate, and N,N′-methylenebisacrylamide.

[0008] Furthermore, in Step 3.2, the diameter of the spinneret holes of the composite spinneret is 0.12 - 0.24 mm, the water - cooling temperature is 35 °C, the water bath length is 2 m, the stretching process is two - stage stretching. Among them, the temperature of the first - stage stretching is 85 °C, and the stretching ratio is 4 times; the temperature of the second - stage stretching is 140 °C, and the stretching ratio is 1.2 times.

[0009] Furthermore, the temperature of heat - setting in Step 3.2 is 150 °C.

[0010] Further, the structural formula of fluorescein O-acrylate in Step 1.1 is as follows: .

[0011] Further, the diameter range of the fluorescently visible polyvinylidene fluoride surgical suture prepared in Step 3 is 0.05 - 0.1 mm, and the average diameter of the fluorescent functional nanospheres prepared in Step 1 is 260 nm.

[0012] A fluorescently visible transparent polyvinylidene fluoride surgical suture is obtained by the above preparation method.

[0013] An application of the fluorescently visible transparent polyvinylidene fluoride surgical suture in biomedicine.

[0014] The application of the above suture in non-therapeutic biomedicine.

[0015] Beneficial effects: Compared with the prior art, the advantages of the present invention are as follows: (1) In the present invention, fluorescein O-acrylate, N,N'-methylenebisacrylamide, and methyl methacrylate are polymerized to obtain fluorescent functional nanospheres. During the synthesis process, there are only water, alcohol, and monomers, without other additives, ensuring the cleanliness of the synthesis process. The average size of the nanospheres is 260 nm. On the one hand, at a relatively low content, it can ensure that the suture has a transparent appearance and mechanical strength, without affecting the original application scenario of the surgical suture; on the other hand, since fluorescein O-acrylate is polymerized into a macromolecule, there is no problem of migration and precipitation, thus 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 doctors and ensuring the accuracy and effectiveness of suturing; (2) The fluorescently visible transparent polyvinylidene fluoride surgical suture prepared by the present invention using the composite molding method has a pure polyvinylidene fluoride resin outer layer, which further avoids the risks of biocompatibility and biotoxicity caused by the addition of fluorescent functional nanospheres. At the same time, it retains the surface characteristics of the polyvinylidene fluoride resin and maintains the original functions such as lubrication and biocompatibility of the surgical suture. Description of the Drawings

[0016] Figure 1 is the transmission electron microscope image of the nanoparticles in the present invention; Figure 2 is the distribution diagram of the nanoparticles in the resin in the present invention; Figure 3 is the suture without adding nanoparticles in the present invention; Figure 4 is the fluorescent suture prepared in the present invention; Figure 5 is the longitudinal section of the fluorescent suture prepared by the present invention; Figure 6 is the cross-section of the fluorescent suture prepared by the present invention. Specific Embodiments

[0017] The technical solution of the present invention will be described in detail below with reference to the accompanying drawings, but the protection scope of the present invention is not limited to the described embodiments.

[0018] Example 1: Step 1: Preparation of fluorescent functional nanospheres 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 absolute ethanol and mixed evenly. 3 g of ammonium persulfate was dissolved in 10 g of water and then added to the reaction system. The reaction system was protected by nitrogen. The reaction was carried out at 75 o °C for 8 hours, followed by centrifugation, washing with water 3 times, and drying to obtain fluorescent functional nanospheres with an average diameter of 260 nm.

[0019] Step 2: Preparation of the blend 10 g of fluorescent functional nanospheres and 4990 g of polyvinylidene fluoride resin were weighed and added to a kneader. Kneading was carried out at 190 °C for 10 minutes, and the rotation speed of the kneader was 50 rpm / min. The blend was obtained by discharging and pelletizing.

[0020] Step 3: Preparation of fluorescent visible transparent polyvinylidene fluoride surgical suture 7 parts of the blend were added to single-screw extruder 1 and sent to the core layer of the composite spinning assembly. 3 parts of polyvinylidene fluoride resin were added to single-screw extruder 2 and sent to the skin layer of the composite spinning assembly. The extrusion temperature was 220 °C / 230 °C / 240 °C. After forming through a composite spinneret with a spinneret hole diameter of 0.12 mm, water cooling, stretching, and heat setting were carried out to obtain a fluorescent visible transparent polyvinylidene fluoride surgical suture with a diameter of 0.05 mm. The water cooling temperature was 35 °C, the water bath length was 2 m, the stretching process was two-stage stretching. Among them, the first-stage stretching temperature was 85 °C, and the stretching ratio was 3.8 times; the second-stage stretching temperature was 140 °C, and the stretching ratio was 1.2 times. The heat setting temperature was 150 °C. The surgical suture was transparent, the mechanical strength was 5.9 cN / dtex, and it had a good luminescence effect under ultraviolet light and was clearly visible to the naked eye.

[0021] In this example, the diameter of the surgical suture was 0.05 mm, and the average diameter of the fluorescent functional nanospheres was 260 nm.

[0022] Example 2 Step 1: Preparation of Fluorescent Functional Nanospheres Add 20 g of fluorescein O-acrylate, 78.5 g of methyl methacrylate, and 1.5 g of N,N′-methylenebisacrylamide to a mixed solution of 625 mL of deionized water and 1875 mL of absolute ethanol. After mixing evenly, add 3 g of ammonium persulfate. The reaction system is protected by nitrogen gas. React at 75 o °C for 8 hours. Then, centrifuge, wash three times with water, and dry to obtain fluorescent functional nanospheres with an average diameter of 260 nm.

[0023] Step 2: Preparation of Blend Weigh 2.5 g of fluorescent functional nanospheres and 4997.5 g of polyvinylidene fluoride resin, add them to a kneader, knead at 190°C for 10 minutes, and the rotation speed of the kneader is 50 rpm / min. Obtain the blend after discharging and pelletizing.

[0024] Step 3: Preparation of Fluorescent Visible Transparent Polyvinylidene Fluoride Surgical Suture Add 5 parts of the blend to single-screw extruder 1 and send it to the core layer of the composite spinning component. Add 5 parts of polyvinylidene fluoride resin to single-screw extruder 2 and send it to the skin layer of the composite spinning component. The extrusion temperature is 220°C / 230°C / 240°C. After forming through a composite spinneret with a spinneret hole diameter of 0.12 mm, cool, stretch, and heat-set to obtain a fluorescent visible transparent polyvinylidene fluoride surgical suture with a diameter of 0.05 mm. The stretching process is two-stage stretching. Among them, the temperature of the first-stage stretching is 85°C, and the stretching ratio is 3.8 times; the temperature of the second-stage stretching is 140°C, and the stretching ratio is 1.2 times. The heat-setting temperature is 150°C.

[0025] The surgical suture is transparent, with a mechanical strength of 5.7 cN / dtex, and has a good luminescent effect under ultraviolet light, which is clearly visible to the naked eye.

[0026] Example 3 Step 1: Preparation of Fluorescent Functional Nanospheres Add 15 g of fluorescein O-acrylate, 85 g of methyl methacrylate, and 1.5 g of N,N′-methylenebisacrylamide to a mixed solution of 625 mL of deionized water and 1875 mL of absolute ethanol. After mixing evenly, add 3 g of ammonium persulfate. The reaction system is protected by nitrogen gas. React at 75 o °C for 8 hours. Then, centrifuge, wash three times with water, and dry to obtain fluorescent functional nanospheres with an average diameter of 260 nm.

[0027] Step 2: Preparation of Blend Weigh 5 g of fluorescent functional nanospheres and 4995 g of polyvinylidene fluoride resin, add them to a kneader, knead at 190 °C for 10 minutes, with the kneader speed at 50 rpm / min, and obtain a blend through discharging and pelletizing.

[0028] Step 3: Preparation of fluorescent visible transparent polyvinylidene fluoride surgical suture Add 6 parts of the blend to single-screw extruder 1 and send it to the core layer of the composite spinning component. Add 4 parts of polyvinylidene fluoride resin to single-screw extruder 2 and send it to the skin layer of the composite spinning component. The extrusion temperature is 220 °C / 230 °C / 240 °C. After forming through a composite spinneret with a spinneret hole diameter of 0.24 mm, cool, stretch, and heat-set to obtain a fluorescent visible transparent polyvinylidene fluoride surgical suture with a diameter of 0.1 mm. The stretching process is two-stage stretching. Among them, the first-stage stretching temperature is 85 °C, and the stretching ratio is 3.8 times; the second-stage stretching temperature is 140 °C, and the stretching ratio is 1.2 times. The heat-setting temperature is 150 °C.

[0029] The surgical suture is transparent, with a mechanical strength of 5.4 cN / dtex, and has a good luminous effect under ultraviolet light, which can be clearly visible to the naked eye.

[0030] Comparative Example 1 The difference from Example 1 is that: in Step 2, weigh 15 g of fluorescent functional nanospheres and 4985 g of polyvinylidene fluoride resin, so that the mass percentage content of fluorescent functional nanospheres in the blend reaches 0.3%. The results show that the surgical suture has a white inner core, is visually opaque, and has a mechanical strength of 5.6 cN / dtex.

[0031] Comparative Example 2 The difference from Example 1 is that: in Step 2, weigh 2 g of fluorescent functional nanospheres and 4998 g of polyvinylidene fluoride resin, so that the mass percentage content of fluorescent functional nanospheres in the blend reaches 0.04%.

[0032] The surgical suture is transparent, but the luminescence under ultraviolet light is not significant and is difficult to identify with the naked eye, and the mechanical strength is 5.7 cN / dtex.

[0034] Experimental Example 1 Conduct experiments on the suture diameters (mm), knot-breaking forces (N), elongation rates (%), strengths (N), and strengths (cN / dtex) of the sutures prepared in Examples 1 to 3 according to the non-absorbable surgical suture industry standard YY / T0167-2020. The results are shown in the following table.

[0035] The results of Example 1 are as follows:

[0036] The results of Example 2 are as follows:

[0037] The results of Example 3 are as follows:

[0038] As described above, although the present invention has been shown and described with reference to specific preferred embodiments, it should not be construed as a limitation of the present invention itself. Various changes in form and detail may be made without departing from the spirit and scope of the present invention as defined by the appended claims.

Claims

1. A preparation method of a fluorescent visible transparent polyvinylidene fluoride surgical suture, characterized by comprising the following steps: Step 1: Prepare nano-microspheres with fluorescent function 1.

1. Add fluorescein O - acrylate, methyl methacrylate, and N,N′ - methylenebisacrylamide into a mixed solution composed of deionized water and absolute ethanol in a mass ratio of (10 - 20):(78.5 - 88.5):1.5; 1.

2. After being uniformly mixed, an initiator is added, and the reaction system is protected by nitrogen. The reaction is carried out for 8 hours at 75 o °C, followed by centrifugation and washing three times with water, and then drying at 60°C for 24 hours to obtain fluorescent functional nanospheres; Step 2. Prepare the blend 2.

1. Weigh the fluorescent functional nanospheres and polyvinylidene fluoride resin according to the ratio, and add them into a kneader; 2.

2. Knead at 190 °C for 10 minutes, with the kneader speed of 50 rpm / min. After discharging and pelletizing, the blend is obtained; the mass ratio range of the fluorescent functional nanospheres to the polyvinylidene fluoride resin is (0.05~0.2):(99.8~99.95); Step 3. Prepare a fluorescent - visible transparent polyvinylidene fluoride surgical suture 3.

1. Add the blend prepared in Step 2 into Single - screw Extruder 1 and send it to the core - layer channel of the composite spinning component. Add polyvinylidene fluoride resin into Single - screw Extruder 2 and send it to the skin - layer channel of the composite spinning component. The three - zone temperature of the extruder is 220 °C / 230 °C / 240 °C; 3.

2. After forming through the composite spinneret plate, it is cooled by water cooling, stretched, and heat - set to obtain a fluorescent - visible transparent polyvinylidene fluoride surgical suture with a core layer and a skin layer.

2. The preparation method of a fluorescent - visible transparent polyvinylidene fluoride surgical suture according to Claim 1, wherein: in Step 1.1, the volume ratio of the deionized water to the absolute ethanol is 1:3, the mass ratio of the total mass of fluorescein O - acrylate, methyl methacrylate, and N,N′ - methylenebisacrylamide 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 fluorescein O - acrylate, methyl methacrylate, and N,N′ - methylenebisacrylamide.

3. The preparation method of a fluorescent visible transparent polyvinylidene fluoride surgical suture according to claim 1, characterized in that: The diameter of the spinneret holes of the composite spinneret plate in Step 3.2 is 0.12 - 0.24 mm, the water - cooling temperature is 35 °C, the water - bath length is 2 m, the stretching process is two - stage stretching, wherein the temperature of the first - stage stretching is 85 °C and the stretching ratio is 4 times; the temperature of the second - stage stretching is 140 °C and the stretching ratio is 1.2 times.

4. The preparation method of a fluorescent visible transparent polyvinylidene fluoride surgical suture according to claim 1, characterized in that: The temperature of the heat - setting in Step 3.2 is 150 °C.

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

7. A fluorescent visible transparent polyvinylidene fluoride surgical suture, characterized in that: Obtained by the preparation method according to any one of Claims 1~5.

8. The application of the fluorescent - visible transparent polyvinylidene fluoride surgical suture described in Claim 7 in biomedicine.

9. The application of a suture according to Claim 8 in non - therapeutic - purpose biomedicine.

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