Graphene-modified antibacterial hernia patch composite screen cloth fabric and preparation method thereof

Abstract

The invention discloses a graphene-modified antibacterial hernia patch composite screen cloth fabric and a preparation method thereof, and belongs to the technical field of surface modification of high polymer material fabrics. The fabric is composed of high polymer material multifilament woven mesh cloth and graphene modified on the fiber surface of the high polymer material multifilament woven mesh cloth. The preparation method comprises the following steps: firstly dissolving graphene oxide in a solvent to prepare a suspension, and then carrying out chemical reduction; then stranding two strands of high polymer material monofilaments to form multifilaments, and weaving the multifilaments into mesh cloth; and finally, under the inert gas atmosphere, the net cloth is arranged above the reduced mixed solution to be subjected to low-temperature fumigation treatment and dried. Graphene is firmly modified on the surface of the multifilament through a fumigation method, and the technological process is simple and controllable. Compared with a traditional monofilament fabric, the obtained multifilament fabric is softer, small in stress response after implantation, high in strength, good in durability and lasting and broad-spectrum in antibacterial function, and the postoperative infection risk is effectively reduced.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer material fabric surface modification, and particularly relates to a graphene modified antibacterial hernia patch multifilament mesh fabric and a preparation method thereof. BACKGROUND

[0002] At present, the researches on the hernia patch mesh fabric at home and abroad are mostly concentrated in the researches on the clinical application performance and physical performance, and less involve the researches on the raw material composition ratio parameters, multifilament structure design, mesh fiber surface modification and post-finishing process of the hernia patch mesh fabric.

[0003] The three medical device products of the hernia patch fabric which have been certified by the China Food and Drug Administration are mainly prepared from the mesh structure of monofilament material, and the main material is the non-absorbable polypropylene fiber woven or the single non-absorbable polypropylene monofilament and single absorbable poly(L-lactide) monofilament. The product is sterilized by epoxy acetylene and used once. The polypropylene fiber has a hard touch, the monofilament woven mesh fabric is not soft enough, and lacks antibacterial function, thereby increasing the risk of postoperative infection of the patient.

[0004] At present, the hernia patch fabric used in the clinic is woven from high molecular materials, and the material itself does not have antibacterial function, is easily polluted by bacteria in the air environment during the operation process, and is easily infected after being implanted in the human body for a long time, so that the antibacterial function of the hernia mesh fabric is particularly important in the clinic.

[0005] Antibacterial mechanism of graphene: the surface of graphene contains rich oxygen-containing functional groups (hydroxyl, carboxyl, epoxy, etc.), these functional groups make the surface of graphene oxide carry negative electricity, and after contacting with the phospholipid layer of the bacterial surface, hydrogen bonds are formed and electrostatic adsorption effect is generated, even if the flagella of the bacteria have a certain movement ability, it is also difficult to escape the bondage. The electrostatic effect also affects the membrane potential of the cell membrane, causing functional damage of the membrane; and the functional groups at the edge of graphene enter the inside of the bacteria after cutting the cell membrane of the bacteria, interact with the respiratory enzyme system, produce reactive oxygen free radicals (ROS) such as hydrogen peroxide, hydroxyl radical and superoxide radical, cause oxidative stress of the bacteria, lead to oxidation of proteins, lipids and nucleic acids, and finally cause membrane aging and bacterial death. The graphene modified antibacterial hernia patch multifilament mesh fabric has long-term antibacterial property.

[0006] Patent CN 112891638 B obtains a hollow tube by an electrospinning method, cuts the electrospinning film with antibacterial effect as a filler in the control tube, makes holes on the hernia patch, and composites the control tube containing the filler and the ordinary hernia patch to achieve antibacterial effect. However, the electrospinning process of this method is complex, the process is more, the product cost is high, and only the antibacterial effect of the hole part is limited, and the whole ordinary hernia patch fabric cannot be effectively antibacterial, Still There are technical After bacterial infection risk. Patent CN 118059310 B is formed by core-shell composite yarn and low-temperature pressure plastic film forming process to obtain a double-sided hernia patch structure. However, due to the two-layer material superposition, the softness of the patch is lost, the stiffness of the patch is increased, and due to the polytetrafluoroethylene film on one side, the original mesh structure of the patch is destroyed, which is not conducive to the flow of liquid and the growth of human tissue. Summary of the invention

[0007] In view of the above problems existing in the prior art, the purpose of the present application is to design a graphene modified antibacterial hernia patch multifilament mesh fabric and its preparation method, which has a simple process and strong operability. The multifilament fabric obtained is softer than the monofilament fabric, has a smaller stress reaction after being implanted into the human body, has high fabric strength, has very good durability, has good antibacterial effect, and has long-lasting antibacterial function.

[0008] The graphene modified antibacterial hernia patch multifilament mesh fabric is characterized by being composed of a high molecular material multifilament woven mesh and graphene modified on the surface of the fiber.

[0009] The graphene modified antibacterial hernia patch multifilament mesh fabric is characterized in that the high molecular material multifilament woven mesh is formed by doubling two high molecular material monofilaments through a weaving device to form multifilament, and then interweaving into a mesh.

[0010] The graphene modified antibacterial hernia patch multifilament mesh fabric is characterized in that the high molecular material in the high molecular material multifilament woven mesh is a non-absorbable material, which is two of polyethylene, polyester, polypropylene, expanded polytetrafluoroethylene, or a composite fabric mixed with the above fibers.

[0011] The graphene modified antibacterial hernia patch multifilament mesh fabric is characterized in that the two high molecular material monofilaments are of different materials, and the mass ratio is 1:1.

[0012] The preparation method of the graphene modified antibacterial hernia patch multifilament mesh fabric is characterized by comprising the following steps: 1) Dissolve graphene oxide in a solvent, the mass ratio of graphene oxide to solvent is 0.5-1.2:50, to obtain a graphene oxide suspension; 2) Perform a chemical reduction reaction on the graphene oxide suspension obtained in step 1) by adding a reducing agent at a temperature of 65-100°C, the mass ratio of graphene oxide suspension to reducing agent is 0.5-2:1, and the reaction time is 12-28 hours; 3) After two high polymer material monofilaments with a mass ratio of 1:1 pass through a braiding device to form a multifilament, the multifilament is interwoven to form a high polymer material multifilament woven mesh; 4) Place the high polymer material multifilament woven mesh prepared in step 3) above the mixed solution after the reduction treatment in step 2) in an inert gas atmosphere, and perform fumigation treatment at 65-100°C for 0.1-2 hours, and then perform drying, to obtain a graphene-modified antibacterial hernia patch multifilament mesh fabric.

[0013] The preparation method of the graphene-modified antibacterial hernia patch multifilament mesh fabric, characterized in that in step 1), the mass ratio of graphene oxide to solvent is 1:50, and the solvent is a 30-70% ethanol aqueous solution, preferably a 50% ethanol aqueous solution.

[0014] The preparation method of the graphene-modified antibacterial hernia patch multifilament mesh fabric, characterized in that in step 2), the reducing agent is at least one of hydriodic acid, hydrazine hydrate, and ethanol, and the mass concentration of the reducing agent is 10%-60%.

[0015] The preparation method of the graphene-modified antibacterial hernia patch multifilament mesh fabric, characterized in that in step 2), the mass ratio of graphene oxide suspension to reducing agent is 1:1, the reaction temperature is 70-85°C, and the reaction time is 15-20 hours.

[0016] The preparation method of the graphene-modified antibacterial hernia patch multifilament mesh fabric, characterized in that in step 4), the fumigation temperature is 80-90°C, the fumigation treatment time is 1-1.5 hours, the drying temperature is 60-80°C, and the drying time is 1-3 hours.

[0017] Compared with the prior art, the graphene-modified antibacterial hernia patch multifilament mesh fabric and the preparation method thereof have the following advantages: 1) Excellent antibacterial performance: through low-temperature fumigation chemical reduction, graphene is firmly and uniformly modified on the surface of each fiber of the multifilament mesh, and the patch is endowed with persistent and broad-spectrum antibacterial function. Tests show that the antibacterial rate of the product of the application on Staphylococcus aureus can reach more than 99.5%, the antibacterial rate on Escherichia coli can reach more than 93.0%, and the antibacterial rate on Candida albicans can reach more than 96.8%.

[0018] 2) Excellent softness and biocompatibility: The use of multifilament structure instead of traditional monofilament, the multifilament is formed by plying multiple fine monofilaments, the fabric is more soft, can significantly reduce the irritation and stress response to the surrounding tissue after implantation, and improve the patient's comfort.

[0019] 3) High strength and durability: The multifilament structure and plying weaving process endow the mesh fabric with higher strength and toughness, so that it can withstand the pressure in the abdominal cavity and has good durability.

[0020] 4) Simple and controllable process, conducive to production: The preparation method avoids complex electrospinning or high-pressure forming process, uses low-temperature fumigation technology, the process is simple, the parameters are easy to control, the equipment requirements are low, it is very suitable for industrial large-scale production, and can ensure the consistency of product performance.

[0021] 5) Maintain the mesh structure: The modification method is only carried out on the surface of the fiber, without damaging the original three-dimensional porous structure of the mesh, which is conducive to the flow of tissue fluid and the growth of fibroblasts, and promotes tissue healing and integration. DETAILED DESCRIPTION

[0022] The present application will be described in detail below in conjunction with specific embodiments. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0023] Example 1 1) Preparation of graphene oxide suspension: 0.5g of graphene oxide was weighed and added to 50g of 50% ethanol aqueous solution, ultrasonic dispersion for 30 minutes to obtain a uniform graphene oxide suspension; 2) Chemical reduction: 50g of 50% hydroiodic acid ethanol solution was added to the graphene oxide suspension obtained in step 1), the reduction temperature was 65℃, and the reduction time was 12h; 3) Multifilament mesh preparation: a polyester monofilament and a polypropylene monofilament were plying formed into a multifilament by a weaving machine according to a mass ratio of 1:1, and then the multifilament was woven into a multifilament mesh fabric; 4) Fumigation-drying: the multifilament mesh fabric prepared in step 3) was suspended above the reaction container containing the reduced solution prepared in step 2), and fumigated at 85℃ under nitrogen atmosphere for 1.0 hour, then the mesh fabric was taken out and dried in a 70℃ oven for 2 hours, to obtain the graphene modified antibacterial hernia patch multifilament mesh fabric.

[0024] Performance testing: Antibacterial tests were conducted according to the oscillation method in GB / T 20944.3-2008. The results showed that the fabric had an inhibition rate of 99.5% against Staphylococcus aureus, 93.0% against Escherichia coli, and 96.8% against Candida albicans.

[0025] Example 2 1) Preparation of graphene oxide suspension: Weigh 1.0g of graphene oxide and add it to 50g of 50% ethanol aqueous solution. Disperse the solution by ultrasonication to prepare a suspension. 2) Chemical reduction: Add 50g of 50% hydroiodic acid hydrazine hydrate solution to the graphene oxide suspension. The reduction temperature is 100℃ and the reduction time is 24h. 3) Preparation of multifilament mesh fabric: Two strands of polypropylene monofilaments are twisted together at a mass ratio of 1:1 using a braiding machine and woven into multifilament mesh fabric. 4) Fumigation-drying: The multifilament mesh fabric is suspended above the reaction vessel containing the reduced solution and fumigated at 100°C under nitrogen for 0.5 hours, and then dried at 80°C for 1.5 hours to obtain the graphene-modified antibacterial hernia patch multifilament mesh fabric.

[0026] Performance testing: Antibacterial rates were 95.1% for Staphylococcus aureus, 90.0% for Escherichia coli, and 93.5% for Candida albicans.

[0027] Example 3 1) Preparation of graphene oxide suspension: Weigh 1.2g of graphene oxide and dissolve it in 50g of 50% ethanol aqueous solution.

[0028] 2) Chemical reduction: Add 50g of hydroiodic acid ethanol solution for reduction. The hydroiodic acid solution contains 25wt% hydroiodic acid and 75wt% ethanol. The reduction temperature is 85℃ and the reduction time is 28h. 3) Preparation of multifilament mesh fabric: Polyethylene and expanded polytetrafluoroethylene monofilaments are twisted together at a mass ratio of 1:1 and woven into multifilament mesh fabric using a weaving machine; 4) Low-temperature fumigation-drying: The multifilament mesh fabric is suspended above a reaction vessel containing the reduced solution and fumigated under nitrogen at 65°C for 2 hours, followed by drying at 60°C for 3 hours to obtain the graphene-modified antibacterial hernia patch multifilament mesh fabric.

[0029] Performance testing: Antibacterial rates were as follows: Staphylococcus aureus 90.0%, Escherichia coli 87.0%, and Candida albicans 91.8%.

[0030] Comparative Example 1 The same polyester / polypropylene multifilament fabric as in Example 1 was used, but without graphene modification.

[0031] Performance testing: Antibacterial tests showed that its inhibition rate against the three tested bacterial species was less than 30%, indicating no significant antibacterial effect.

[0032] The following experimental data further demonstrates the beneficial effects of the present invention.

[0033] Experiment 1: Comparative test of mechanical properties.

[0034] Table 1. Comparison of Mechanical Properties of Example 2 and Monofilament Polypropylene Patch Table 1 shows that, compared with traditional monofilament polypropylene hernia patches, the graphene-modified multifilament mesh fabric prepared in Example 2 of this invention has a significant advantage in mechanical strength. By employing a multifilament structure, this invention not only achieves antibacterial function but also significantly improves the mechanical properties of the hernia patch, giving it higher tensile strength and bursting strength, and better durability.

[0035] Experiment 2: In vitro cytotoxicity test, test sample: Example 2 (sterilization status: sterilized, EO).

[0036] Table 2. Example 2: In vitro cytotoxicity assay - MTT cytotoxicity assay (testing according to GB / T 16886.5-2017) Table 3. Cell Morphology Description Tables 2 and 3 show that, compared with the negative control group (cell survival rate of 92.7%), the L-929 cell survival rate of the sample extract in Example 2 was higher than 83.0% at all concentrations, and the cell morphology observation level was 0 (indicating normal cell morphology and no signs of toxicity). The experimental results show that the graphene-modified hernia patch prepared in this invention has no cytotoxicity and good biocompatibility.

[0037] The beneficial effects described in this invention can also be achieved by conducting the above-mentioned experiments using Embodiments 1 and 3 of this invention.

[0038] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A graphene-modified antibacterial hernia mesh fabric filament screen cloth fabric, characterized in that The graphene is modified on the surface of the fiber of the high polymer material multifilament woven mesh cloth.

2. A graphene-modified antibacterial hernia patch multifilament mesh fabric according to claim 1, characterized in that: The high polymer material multifilament woven mesh cloth is formed by interweaving the multifilament formed by plying two high polymer material filaments through a weaving device.

3. A graphene-modified antibacterial hernia patch multifilament mesh fabric according to claim 1, wherein: The high polymer material in the high polymer material multifilament woven mesh cloth is non-absorbable material, which is polyethylene, polyester, polypropylene, expanded polytetrafluoroethylene or a composite fabric mixed with two of the above fibers.

4. A graphene-modified antibacterial hernia patch multifilament mesh fabric as claimed in claim 2, wherein: The two high polymer material filaments are of different materials, and the mass ratio is 1:

1.

5. The method for preparing a graphene-modified antibacterial hernia patch multifilament fabric as described in claim 1, characterized in that... The method comprises the following steps: 1) Dissolve graphene oxide in a solvent, and the mass ratio of graphene oxide to solvent is 0.5-1.2:50 to obtain a graphene oxide suspension; 2) Add a reducing agent to the graphene oxide suspension obtained in step 1) at a temperature of 65-100°C to perform a chemical reduction reaction, and the mass ratio of graphene oxide suspension to reducing agent is 0.5-2:1, and the reaction time is 12-28 hours; 3) Plying two high polymer material filaments with a mass ratio of 1:1 through a weaving device to form a multifilament, and then interweaving to form a high polymer material multifilament woven mesh cloth; 4) Placing the high polymer material multifilament woven mesh cloth prepared in step 3) above the mixed solution treated by reduction in step 2) in an inert gas atmosphere, and performing fumigation treatment at 65-100°C for 0.1-2 hours, and then drying to obtain an antibacterial hernia patch multifilament mesh fabric modified by graphene.

6. A method of making a graphene-modified antibacterial hernia mesh multifilament mesh fabric according to claim 5, wherein In step 1), the mass ratio of graphene oxide to solvent is 1:50, and the solvent is a 30-70% ethanol aqueous solution, preferably a 50% ethanol aqueous solution.

7. A method of making a graphene-modified antibacterial hernia mesh multifilament mesh fabric according to claim 5, wherein In step 2), the reducing agent is at least one of hydriodic acid, hydrazine hydrate and ethanol, and the mass concentration of the reducing agent is 10%-60%.

8. A method of making a graphene-modified antibacterial hernia mesh multifilament mesh fabric according to claim 5, wherein In step 2), the mass ratio of graphene oxide suspension to reducing agent is 1:1, the reaction temperature is 70-85°C, and the reaction time is 15-20 hours.

9. A method of making a graphene-modified antibacterial hernia mesh multifilament mesh fabric according to claim 5, wherein In step 4), the fumigation temperature is 80-90°C, the fumigation treatment time is 1-1.5 hours, the drying temperature is 60-80°C, and the drying time is 1-3 hours.

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