Surgical auxiliary instrument material with bacteriostatic property and preparation method thereof

Abstract

The application provides a surgical auxiliary instrument material with bacteriostatic performance and a preparation method thereof, relates to the technical field of bacteriostatic medical instruments, and comprises the following steps: heating and mixing polyethylene, polycaprolactone, styrene-butadiene block copolymer and a bacteriostatic precursor to obtain a mixture of the surgical auxiliary instrument material with bacteriostatic performance, and the raw materials of the bacteriostatic precursor include flax lignan, 4-vinyl-2,6-dichlorophenol and imino methacrylate. In view of the problem of poor wear resistance of the bacteriostatic surgical auxiliary instrument, the bacteriostatic precursor with high polymer coating flax lignan is prepared, the compatibility of flax lignan and the remaining high molecular materials (polyethylene, polylactic acid, styrene-butadiene block copolymer) is improved, the interface bonding performance is improved, the synergistic effect between flax lignan and other materials is exerted, the antibacterial substance is no longer a heterogeneous phase particle in the bacteriostatic surgical instrument, and the continuity, wear resistance and oxidation resistance of the whole material are maintained.

Description

Technical Field

[0001] This application relates to the field of antibacterial medical device technology, and more specifically, to a surgical aid material with antibacterial properties and its preparation method. Background Technology

[0002] The concept of aseptic technique originated from the microbiological studies of Pasteur and Leeuwenhoek. British surgeon Lister applied microbiology to medicine, proposing that airborne microorganisms were the cause of wound suppuration and infection, and established a new sterilization method. Over time, aseptic technique has continuously evolved, including the use of steam sterilization of surgical instruments and dressings, and the invention of rubber surgical gloves. Antimicrobial / microbial medical devices, due to their active antimicrobial and bactericidal capabilities, have gradually gained an important position with the development of the aseptic concept. Currently, antimicrobial / microbial medical devices mainly fall into the following categories:

[0003] 1. In vivo effective type

[0004] (1) Drug-loaded type: Chinese invention patent with publication number CN109925535A discloses a targeted drug release interventional medical device, which consists of an interventional medical device and a sustained-release drug coating. The sustained-release drug coating is applied to the surface of the interventional medical device and is composed of drug material, drug carrier material, antibacterial agent, antioxidant and adhesive. The drug exhibits a stable shape in vitro and is released in a targeted manner after implantation into the human body.

[0005] (2) Antibody-based: Chinese invention patent with publication number CN114533954A discloses a method for imparting antibacterial function to the surface of an implantable medical device, as well as the implantable medical device prepared therefrom and the application method, including the following steps: S1: providing an implantable medical device, mixing calcium into the surface of the implantable medical device to form a composite material surface on the implantable medical device, wherein the amount of calcium mixed in the composite material surface is 4 to 30 at.%; S2: reacting the composite material surface with blood at a temperature of 30 to 40°C for a time of 0.5 to 2.0 h, so that proteins with defensive or immune functions in the blood are uniformly adsorbed on the composite material surface.

[0006] 2. In vitro effective type:

[0007] (1) Doped type: Chinese invention patent CN109735042A discloses a medical AMTPS material, medical device, and preparation method, comprising the following raw materials in the following weight ratios: 50-80 parts by weight of styrene-butadiene-styrene block copolymer SEBS, 25-50 parts by weight of reinforcing resin polypropylene PP, 0.05-0.3 parts by weight of green composite antioxidant ECLL, 0.05-0.2 parts by weight of slip agent, 0.005-0.02 parts by weight of anti-adhesive or reinforcing agent, and 0.002-0.02 parts by weight of antibacterial agent. Due to the addition of the composite antioxidant and antibacterial agent, the material itself possesses antibacterial function.

[0008] (2) Antibacterial layer type: Chinese invention patent with publication number CN112575423A discloses a high-strength composite fiber for medical devices. This invention produces a composite fiber for medical devices with high tensile strength and good antibacterial effect by combining hollow carbon fiber core wire, outer hollow carbon fiber, polyester fiber wire, polyurethane bonding strip and nano silver antibacterial layer.

[0009] However, for non-implantable medical devices, even if they have antibacterial properties, they must be thoroughly disinfected and cleaned after use before they can be reused. This poses a challenge to the wear resistance and strength of the devices. Therefore, there is a need for a wear-resistant, high-strength surgical aid material with antibacterial function. Summary of the Invention

[0010] To address the aforementioned issues, this application employs a method for preparing surgical auxiliary instrument materials with antibacterial properties. The method involves heating and mixing polyethylene, polycaprolactone, styrene-butadiene block copolymer, and an antibacterial precursor to obtain a mixture of surgical auxiliary instrument materials with antibacterial properties. The raw materials for the antibacterial precursor include linolenic acid, 4-vinyl-2,6-dichlorophenol, and iminomethacrylate.

[0011] Optionally, the preparation steps of the antibacterial precursor include: adding a solvent to the dried linolenic acid while stirring to dissolve it, then adding 4-vinyl-2,6-dichlorophenol, iminomethacrylate and an initiator in sequence, purging with nitrogen gas, and then heating and stirring the reaction in an oil bath. After the reaction is completed, the product is precipitated with petroleum ether, filtered, and then dried by air and vacuum to obtain the antibacterial precursor.

[0012] Optionally, the antibacterial surgical aid material masterbatch comprises the following raw materials in parts by weight:

[0013] Flax lignans: 5-8 parts;

[0014] Solvent: 20-60 parts;

[0015] 4-Vinyl-2,6-dichlorophenol: 3-7 parts;

[0016] Iminomethacrylate: 1-6 parts;

[0017] Initiator: 0.01-0.5 parts;

[0018] Polyethylene: 80-90 parts;

[0019] Polycaprolactone: 10-20 parts;

[0020] Styrene-butadiene block copolymer: 10-20 parts.

[0021] Optionally, the oil bath temperature is 60-80℃.

[0022] Optionally, the initiator is a combination of four materials in a mass ratio of benzoyl peroxide, azobisisobutyronitrile, mercaptoethanol, and sodium lauryl sulfate in a ratio of 5:2:2:1.

[0023] Optionally, the solvent is one of dimethyl sulfoxide, isopropanol, butyl acetate, chloroform, tetrahydrofuran, and acetone.

[0024] Optionally, the mixture is extruded and granulated to obtain antibacterial surgical aid material masterbatch. When the antibacterial surgical aid material masterbatch is used by injection molding, the injection molding temperature is 180-200℃.

[0025] Optionally, the molecular weight of polyethylene is 400,000-500,000, the molecular weight of polycaprolactone is 10,000-80,000, and the molecular weight of styrene-butadiene block copolymer is 30,000-100,000.

[0026] Optionally, the heating and mixing temperature is 200-240℃.

[0027] This application also provides a surgical aid material with antibacterial properties, which is prepared by any of the aforementioned methods for preparing surgical aid materials with antibacterial properties.

[0028] The beneficial effects of the surgical auxiliary instrument material with antibacterial properties and its preparation method provided in this application are as follows:

[0029] To address the issue of antibacterial properties but poor wear resistance in surgical aids, an antibacterial precursor material with antibacterial activity was first prepared. Using a self-developed antibacterial monomer polymerization reaction system, an antibacterial precursor with polymer-coated linolenic acid was prepared. This not only endows the surgical aid material with antibacterial properties, but also, thanks to the presence of polymers on the surface of linolenic acid, improves the compatibility of linolenic acid with other polymeric materials (polyethylene, polylactic acid, styrene-butadiene block copolymer), enhancing interfacial bonding performance. This allows for better synergistic effects between linolenic acid and other materials, preventing the antibacterial substance from becoming heterogeneous particles within the antibacterial surgical instrument, maintaining the overall continuity of the material, and improving the antibacterial, wear-resistant, and antioxidant properties of the surgical aid.

[0030] To address the shortcomings in the injection molding performance of surgical aids, particularly issues such as porosity, shrinkage cavities, warpage, and uneven coloring that affect clinical use, the following approach is adopted. Firstly, a method using antibacterial monomers and linseed lignans to establish antibacterial precursors solves the problems of insufficient antibacterial monomer performance and poor interfacial bonding between linseed lignans and other polymers. This improves the interfacial bonding performance between the antibacterial monomer and the polymer, thereby enhancing the injection molding properties of the material. Secondly, polyethylene, polycaprolactone, and styrene-butadiene block copolymers are used as the matrix components of the surgical aids provided in this application. The good flowability of polycaprolactone and styrene-butadiene block copolymers, along with improved flow behavior through blending modification, enables high-performance extrusion. The high segmental entanglement of polyethylene, polycaprolactone, and styrene-butadiene block copolymers exhibits significantly increased strength, which is beneficial for improving both injection molding performance and wear resistance. Detailed Implementation

[0031] To make the technical problems, technical solutions, and beneficial effects to be solved by this application clearer, the following detailed description is provided in conjunction with embodiments. It should be understood that the specific embodiments described herein are merely illustrative of this application and are not intended to limit this application.

[0032] Example 1

[0033] (1) Preparation of antibacterial precursor

[0034] 5g of dried linolenic acid was placed in a round-bottom flask, and 20g of dimethyl sulfoxide was added to dissolve it while stirring. Then, 3g of 4-vinyl-2,6-dichlorophenol and 1g of iminomethacrylate were added sequentially, followed by 0.01g of initiator. Nitrogen gas was purged for 30 minutes, and then the mixture was placed in an oil bath at 60°C for 8 hours with stirring during the reaction. After the reaction was completed, the product was precipitated with petroleum ether to obtain the reaction product. The product was dried in air and then vacuum dried to obtain the antibacterial precursor.

[0035] The initiator is a combination of four materials in a mass ratio of benzoyl peroxide, azobisisobutyronitrile, mercaptoethanol and sodium lauryl sulfate in a ratio of 5:2:2:1.

[0036] (2) Preparation of antibacterial surgical aid materials

[0037] 80g of polyethylene, 10g of polycaprolactone, 10g of styrene-butadiene block copolymer and antibacterial precursor were poured into the mixing chamber of a high-speed mixer and heated to 200℃. After heating and mixing, a mixture was obtained. The molecular weight of polyethylene was 200,000-500,000, the molecular weight of polycaprolactone was 10,000-80,000, and the molecular weight of styrene-butadiene block copolymer was 30,000-100,000.

[0038] (3) Extrusion granulation

[0039] The mixture is poured into a twin-screw extruder for extrusion granulation. After extrusion, cooling in a water bath, and drying, it enters a pelletizer for granulation to obtain antibacterial surgical auxiliary instrument material masterbatch.

[0040] (4) Injection molding

[0041] The obtained antibacterial surgical aid material masterbatch was poured into an injection molding machine, and the temperature of the injection molding machine was controlled at 180℃ to perform injection molding of surgical aid sample.

[0042] (5) Performance testing

[0043] The antibacterial performance was tested according to the carrier antibacterial test in WS / T 650-2019 "Evaluation Method for Antibacterial and Bacteriostatic Effects". WS / T 650-2019 specifies the evaluation method for antibacterial and bacteriostatic effects, mainly including the calculation of the inhibition rate and the determination of the results. The formula for calculating the inhibition rate (X) is: X = (A0 - A1) / A0 × 100%, where A0 is the amount of bacteria recovered in the positive control group, and A1 is the amount of bacteria recovered in the experimental group.

[0044] The standard for tensile testing is GB / T 1040.1-2018, "Determination of Tensile Properties of Plastics". This standard specifies the specimens, testing equipment, testing conditions, and methods for processing test results for plastic tensile testing.

[0045] Wear resistance was tested according to GB / T 5478-2008 "Test Method for Rolling Abrasion of Plastics", and the wear rate was determined. The cross-sectional area of ​​each specimen was measured four times at different locations on the wear track, and the average value was taken. The wear volume was obtained by multiplying the average cross-sectional area by the wear track length. V, will Substituting V into the following formula, we can obtain the volumetric wear rate: W= V / FS.

[0046] The aging test was conducted according to GB / T 16422 "Laboratory Light Source Exposure Test Method for Plastics" with an aging time of 500 hours. The tensile properties of the aged samples were then tested, and the change in tensile strength was measured to compare the aging resistance of the samples.

[0047] Example 2

[0048] The difference from Example 1 is that the amount of flax lignan added is 6g, the amount of 4-vinyl-2,6-dichlorophenol added is 4g, the amount of iminomethacrylate added is 2g, the solvent is isopropanol with a mass of 30g, the amount of initiator added is 0.1g, the amount of polyethylene added is 85g, the amount of polycaprolactone added is 15g, the amount of styrene-butadiene block copolymer added is 15g, the oil bath temperature is 65℃, the heating and mixing temperature is 210℃, and the injection molding machine temperature during sample preparation is 185℃.

[0049] Example 3

[0050] The difference from Example 1 is that the amount of flax lignan added is 7g, the amount of 4-vinyl-2,6-dichlorophenol added is 5g, the amount of iminomethacrylate added is 3g, the solvent is butyl acetate with a mass of 40g, the amount of initiator added is 0.2g, the amount of polyethylene added is 90g, the amount of polycaprolactone added is 20g, the amount of styrene-butadiene block copolymer added is 20g, the oil bath temperature is 70℃, the heating and mixing temperature is 220℃, and the injection molding machine temperature during sample preparation is 190℃.

[0051] Example 4

[0052] The difference from Example 1 is that the amount of flax lignan added is 8g, the amount of 4-vinyl-2,6-dichlorophenol added is 6g, the amount of imino methacrylate added is 4g, the solvent is chloroform with a mass of 50g, the amount of initiator added is 0.3g, the oil bath temperature is 75°C, the heating and mixing temperature is 230°C, and the injection molding machine temperature during sample preparation is 195°C.

[0053] Example 5

[0054] The difference from Example 1 is that the amount of 4-vinyl-2,6-dichlorophenol added is 7g, the amount of iminomethacrylate added is 5g, the solvent is tetrahydrofuran, the solvent mass is 60g, the amount of initiator added is 0.4g, the oil bath temperature is 80℃, the heating and mixing temperature is 240℃, and the injection molding machine temperature during sample preparation is 200℃.

[0055] Example 6

[0056] The difference from Example 1 is that the amount of imino methacrylate added is 6g, the solvent is acetone, and the amount of initiator added is 0.5g.

[0057] Table 1. Statistical table of reaction parameters and products

[0058]

[0059] Table 1 (continued) Statistical table of reaction parameters and products

[0060]

[0061] As shown in Table 1, the addition of the antibacterial precursor did not significantly affect the performance of the surgical aid material with antibacterial properties provided in this application.

[0062] The above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application 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. Such 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 this application, and should all be included within the protection scope of this application.

Claims

1. A method for the production of a surgical aid material having bacteriostatic properties, characterized in that: The polyethylene, polycaprolactone, styrene-butadiene block copolymer and bacteriostatic precursor are heated and mixed to obtain a mixture of the surgical auxiliary instrument material with bacteriostatic property, the mixture is extruded and granulated to obtain the bacteriostatic surgical auxiliary instrument material master batch, raw materials of the bacteriostatic precursor include flax lignan, 4-vinyl-2,6-dichlorophenol and imino methacrylate; The preparation steps of the bacteriostatic precursor include: adding a solvent to the dried flax lignan for dissolution with stirring, then sequentially adding 4-vinyl-2,6-dichlorophenol, imino methacrylate and an initiator, introducing nitrogen, then heating and stirring in an oil bath for reaction, after the reaction is completed, the reaction product is precipitated with petroleum ether, filtered, and then air dried and vacuum dried to obtain the bacteriostatic precursor.

2. The method for producing a surgical auxiliary instrument material having a bacteriostatic property according to claim 1, characterized by: The bacteriostatic surgical auxiliary instrument material master batch includes the following raw materials in parts by weight: Flax lignan: 5-8 parts; Solvent: 20-60 parts; 4-vinyl-2,6-dichlorophenol: 3-7 parts; Imino methacrylate: 1-6 parts; Initiator: 0.01-0.5 parts; Polyethylene: 80-90 parts; Polycaprolactone: 10-20 parts; Styrene-butadiene block copolymer: 10-20 parts.

3. The method for producing a surgical auxiliary instrument material having a bacteriostatic property according to claim 1, characterized by: The oil bath temperature is 60-80℃.

4. The method for preparing a surgical auxiliary instrument material having a bacteriostatic property according to claim 1, wherein: The initiator is a combination of benzoyl peroxide, azobisisobutyronitrile, mercaptoethanol and sodium lauryl sulfate in a mass ratio of 5:2:2:

1.

5. The method for preparing a surgical auxiliary instrument material having a bacteriostatic property according to claim 1, wherein: The solvent is one of dimethyl sulfoxide, isopropyl alcohol, butyl acetate, chloroform, tetrahydrofuran and acetone.

6. The method for preparing a surgical auxiliary instrument material having a bacteriostatic property according to claim 1, wherein: When the bacteriostatic surgical auxiliary instrument material master batch is used by injection molding, the injection molding temperature is 180-200℃.

7. The method for producing a surgical auxiliary instrument material having a bacterium-inhibiting property according to claim 1, wherein: The molecular weight of the polyethylene is 400000-500000, the molecular weight of the polycaprolactone is 10000-80000, and the molecular weight of the styrene-butadiene block copolymer is 30000-100000.

8. The method for preparing a surgical auxiliary instrument material having a bacteriostatic property according to Claim 1, wherein: The heating and mixing temperature is 200-240℃.

9. A surgical aid material having bacteriostatic properties, characterized by: Prepared by the method of any one of claims 1-8. The surgical auxiliary instrument material with bacteriostatic property prepared by the method of any one of claims 1-8.

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