Composite fiber for surgical gown and preparation method of composite fiber

Abstract

The invention belongs to the technical field of composite fibers, and particularly relates to a composite fiber for surgical gown and a preparation method thereof. Polypropylene and polyethylene glycol terephthalate are adopted as base material raw materials, so that the toughness and chemical resistance of the composite fiber are improved, and the medical sterilization treatment frequency of the surgical gown is increased; the organic nano antibacterial agent, the modified nano silver powder and the inulin are adopted to jointly form the composite antibacterial agent, and the broad-spectrum antibacterial effect is achieved by means of complementary advantages and synergistic interaction of all the components; a mixture of an ionic polymer and graphene oxide is adopted as an antistatic agent, a conductive network is formed in the fiber, and the antistatic performance of the fiber is improved.

Description

Technical Field

[0001] This invention belongs to the field of composite fiber technology, specifically relating to a surgical composite fiber and its preparation method. Background Technology

[0002] Currently, the methods for achieving antibacterial and antistatic functions in surgical gown fibers mainly focus on two approaches: single-fiber modification and surface coating with auxiliaries. However, both methods have significant technical drawbacks, making it difficult to simultaneously meet the requirements of performance stability and medical safety after long-term use and repeated sterilization. The single-fiber modification approach primarily involves adding inorganic antibacterial agents (such as nano-silver and zinc oxide) or mixing in quaternary ammonium salt antistatic agents during fiber preparation, attempting to build a functional system from within the fiber. However, the uniformity of antibacterial agent dispersion in the resulting antibacterial fibers is difficult to control. When the amount of antibacterial agent added is insufficient, it cannot achieve long-term inhibition of common pathogenic microorganisms such as Escherichia coli and Staphylococcus aureus, easily leading to localized bacterial growth; excessive addition will damage the mechanical properties of the fiber itself, causing the surgical gown to easily tear and deform after repeated washing and stretching, shortening its service life. Regarding the surface coating with auxiliaries approach, the industry mostly adopts post-processing techniques, spraying or impregnating antibacterial agents, antistatic agents, or composite functional finishing agents onto the surface of the fiber or fabric. For example, by using polyurethane resin as a carrier to coat the surface of pure cotton or polyester surgical gowns with antimicrobial peptides and cationic surfactants, surface antibacterial and antistatic effects can be quickly achieved. However, in this method, the bonding force between the functional layer and the fiber surface is weak. After repeated washing, high-temperature and high-pressure sterilization, ethylene oxide sterilization and other commonly used medical treatment processes, the surface functional coating is prone to peeling off and powdering. This not only leads to a sharp decline in antibacterial and antistatic properties, but the peeled coating particles may also contaminate the surgical area, causing a risk of secondary infection. Furthermore, the surface coating can easily clog the fiber pores, damaging the original breathability and moisture absorption of the surgical gown, causing discomfort such as stuffiness and sweat accumulation for medical staff after wearing it.

[0003] Chinese patent application CN116695286A discloses a method for preparing quaternary ammonium salt antibacterial fibers. Specifically, the method involves: mixing methanol and epoxybromopropane to obtain solvent 1; mixing quaternary ammonium salt with methanol to obtain solvent 2; adding solvent 1 dropwise to solvent 2 for a single reaction, removing methanol to obtain a product, recrystallizing the product, and vacuum drying to obtain a quaternary ammonium salt intermediate; mixing the quaternary ammonium salt intermediate, dextran, NaOH, and water for a second reaction, adjusting the pH, dialyzing, and freeze-drying to obtain the quaternary ammonium salt antibacterial fibers. This method uses quaternary ammonium salt grafted with dextran to achieve antibacterial properties. However, the grafting bond between quaternary ammonium salt and dextran is weak, and no cross-linking reinforcement treatment is performed during preparation. After high-temperature steam and ethylene oxide sterilization, the grafted quaternary ammonium salt is prone to detachment and degradation, leading to a sharp decline in antibacterial performance. Furthermore, the antibacterial fibers disclosed in this method have not undergone antistatic modification. Although quaternary ammonium salts can act as mild antistatic agents, their cationic sites are mainly used for antibacterial effects, resulting in high electrostatic leakage resistance of the fibers, which cannot meet the requirements of surgical gowns for antistatic fibers. Summary of the Invention

[0004] To address the technical problems of poor antibacterial and antistatic properties in the prior art, this invention provides a surgical surgical composite fiber and its preparation method.

[0005] To achieve the above objectives, the technical solution of the present invention is as follows: A method for preparing surgical composite fibers specifically involves: mixing polypropylene, polyethylene terephthalate, composite antibacterial agent, antistatic agent, plasticizer and antioxidant evenly, melting and extruding to obtain a composite fiber spinning solution, then performing melt spinning through a spinneret, cooling and then stretching, heat setting, cooling, washing with water, and drying to obtain surgical composite fibers. The composite antibacterial agent is composed of organic nano antibacterial agent, modified nano silver powder, and inulin in a mass ratio of (8-11):(3-5):(1-2).

[0006] In the above scheme, using polypropylene and polyethylene terephthalate as the base materials for the composite fiber gives it good toughness and chemical resistance. Polyethylene terephthalate possesses high strength and high-temperature resistance; when mixed with polypropylene, the fiber's breaking strength and abrasion resistance are significantly improved, enabling it to stably withstand high-temperature steam, ethylene oxide, and other commonly used medical sterilization treatments. By adding antibacterial and antistatic agents to the composite fiber spinning solution, the composite fiber achieves highly efficient, broad-spectrum antibacterial, and long-lasting antistatic effects. Furthermore, after multiple washes and sterilizations, no antibacterial or antistatic agents are shed, preventing the degradation of antibacterial and antistatic effects.

[0007] A composite antibacterial agent is composed of organic nano-antibacterial agent, modified nano-silver powder and inulin. By leveraging the complementary advantages and synergistic effects of each component, a broad-spectrum antibacterial effect is achieved. At the same time, the extensive use of organic nano-antibacterial agent and modified nano-silver powder can effectively improve the dispersion uniformity of the composite antibacterial agent in the fiber, ensuring rapid sterilization and long-lasting antibacterial effect while reducing the impact of the composite antibacterial agent on the mechanical properties of the fiber.

[0008] Further, the preparation method of the organic nano-antibacterial agent is as follows: Nano-titanium dioxide powder and 3-chloropropionyl chloride are added to ethyl acetate, and the mixture is heated to 45-55℃ under nitrogen protection, sealed, and stirred for 6-8 hours. After centrifugation and washing, activated nano-titanium dioxide powder is obtained. Anhydrous ethanol and dimethyl sulfoxide mixed solvent are added to a reaction vessel, followed by the addition of activated titanium dioxide powder. The mixture is then ultrasonically dispersed, and polyethyleneimine is added. The mixture is heated to 65-75℃, stirred under nitrogen protection for 20-24 hours, centrifuged, washed, and dried to obtain an antibacterial agent intermediate. Dioxane is added to the reaction vessel, and the antibacterial agent intermediate is added under nitrogen protection. The mixture is ultrasonically dispersed, and bromooctane is added. The mixture is heated to 55-65℃, sealed, and stirred for 8-10 hours. The mixture is then cooled to 30-35℃, and dimethyl sulfate is added. The mixture is sealed and stirred for 4-6 hours, centrifuged, washed, and dried to obtain the organic nano-antibacterial agent.

[0009] In the above scheme, nano-titanium dioxide powder is used as an inorganic carrier. A multi-site synergistic bactericidal organic nano-antibacterial agent is prepared through acyl chloride activation reaction, polyethyleneimine grafting reaction, and quaternization modification. Nano-titanium dioxide has a high specific surface area, which can significantly increase the contact area with bacteria and improve antibacterial efficiency. The polyethyleneimine molecular chain contains a large number of long-chain alkyl groups and cationic quaternary ammonium groups. The long-chain alkyl groups have strong hydrophobicity and can quickly insert into the phospholipid bilayer of the bacterial cell membrane, disrupting the orderly arrangement of the cell membrane. The cationic quaternary ammonium groups synergistically interact with the residual amino groups in the polyethyleneimine molecule, breaking down the bacterial cell membrane through electrostatic interaction to achieve a highly efficient bactericidal effect. Simultaneously, the organic nano-antibacterial agent can enter the cell through the damaged cell membrane, blocking nucleic acid replication and protein synthesis processes, inhibiting bacterial growth and reproduction from the root. A broad-spectrum antibacterial effect is achieved through multiple mechanisms of physical destruction and chemical metabolic blockade.

[0010] Furthermore, in the preparation method of the organic nano antibacterial agent, the mass ratio of ethyl acetate, nano titanium dioxide powder, and 3-chloropropionyl chloride is (20-25):(1-1.5):(0.3-0.5); the volume ratio of anhydrous ethanol to dimethyl sulfoxide in the mixed solvent of anhydrous ethanol and dimethyl sulfoxide is 3:1, and the mass ratio of the mixed solvent of anhydrous ethanol and dimethyl sulfoxide, activated titanium dioxide powder, and polyethyleneimine is 30:(1-1.5):(0.7-0.8); the mass ratio of dioxane, antibacterial agent intermediate, bromooctane, and dimethyl sulfate is 40:(1-1.3):(0.5-0.7):(0.3-0.5).

[0011] Furthermore, the preparation method of the modified nano-silver powder is as follows: anhydrous ethanol is added to a reaction vessel, nano-silver powder is added under stirring, and ultrasonic dispersion is performed. γ-methacryloyloxypropyltrimethoxysilane is added under stirring, the pH value is adjusted to 4.0-5.0, the mixture is heated to 60-70℃, stirred for 3-5 hours, cooled, centrifuged, washed, dried, cooled, and ground to obtain the modified nano-silver powder.

[0012] In the above scheme, γ-methacryloxypropyltrimethoxysilane is used to modify the nano-silver. Taking advantage of the high similarity between the methacryloxy group in the γ-methacryloxypropyltrimethoxysilane molecule and the ester group in the polyethylene terephthalate molecule, the dispersibility of nano-silver in polyethylene terephthalate is effectively improved. At the same time, the binding force between γ-methacryloxypropyltrimethoxysilane and the hydroxyl groups on the surface of nano-silver is very strong. After hydrolysis, stable Si-O-Ag bonds are formed, which effectively prevents the precipitation of antibacterial agents from nano-silver and ensures the long-term stability of the antibacterial properties of the composite fiber.

[0013] Furthermore, in the preparation method of modified nano-silver powder, the mass ratio of anhydrous ethanol, nano-silver powder, and γ-methacryloyloxypropyltrimethoxysilane is (8-10):1:(0.5-0.8).

[0014] Furthermore, the antistatic agent is a mixture of an ionic polymer and graphene oxide.

[0015] In the above scheme, an antistatic agent is composed of ionic polymers and graphene oxide. The ionic polymers adsorb onto the surface of graphene oxide, effectively preventing the graphene oxide sheets from stacking and agglomerating through steric hindrance and electrostatic repulsion. The ionic polymers are uniformly dispersed between the graphene oxide sheets, acting as conductive bridges to connect isolated graphene oxide sheets and form a conductive network, thus improving the antistatic properties of the fiber. Furthermore, the very sharp edges of the graphene oxide nanosheets can pierce the cell membranes of bacteria, causing physical damage. This can synergistically enhance the antibacterial properties of the fiber with the composite antibacterial agent.

[0016] Furthermore, the preparation method of the antistatic agent is as follows: terephthalic acid, sodium 5-sulfonate dimethyl isophthalate, ethylene glycol, N,N-dimethylformamide, and graphene oxide are added to a reaction vessel and mixed evenly. Tetrabutyl titanate and phosphoric acid are added, and after stirring evenly, the reaction system pressure is controlled at 0.1-0.3 MPa under nitrogen protection. The temperature is raised to 160-180℃ and stirred for 1-2 hours. Then, the temperature is raised to 200-220℃ and stirred for 3-4 hours. The temperature is raised to 240-260℃, the pressure is reduced to 0.05-0.08 MPa, and stirred for 1-2 hours. The pressure is reduced to 0.001-0.005 MPa and stirred for 4-6 hours. The temperature is lowered to 180-200℃ and then restored to normal pressure. The mixture is dried, added to anhydrous ethanol, stirred and soaked for 24 hours, and repeated 3-4 times. After drying, cooling, and grinding, the antistatic agent is obtained.

[0017] In the above scheme, the sulfonate groups of sodium 5-sulfonate dimethyl isophthalate are embedded into the polyester backbone through a copolymerization reaction. The sulfonate groups have extremely strong hygroscopic properties, adsorbing water molecules from the air or skin surface to form a continuous water film on the fiber surface. This dissolves ions ionized from the antistatic agent, forming an ionic conductor and effectively improving the antistatic properties of the composite fiber. Furthermore, the addition of graphene oxide during the preparation process allows the polymer molecular chains to interweave within the graphene oxide, fixing and dispersing it, and forming a synergistic conductive network. This not only enhances the antistatic effect but also reduces the surface resistance of the composite fiber, improving the dispersion performance of graphene oxide within the composite fiber.

[0018] Furthermore, the weight percentages of each component in the preparation method of the antistatic agent are as follows: 40-47 parts of terephthalic acid, 5-10 parts of sodium 5-sulfonate dimethyl isophthalate, 50-60 parts of ethylene glycol, 10-15 parts of N,N-dimethylformamide, 10-15 parts of graphene oxide, 1-5 parts of tetrabutyl titanate, and 3-8 parts of phosphoric acid.

[0019] Furthermore, the plasticizer is dibutyl phthalate; the antioxidant is antioxidant 1010; and the weight parts of each component in the preparation method of the surgical composite fiber are: 5-10 parts of polypropylene, 40-50 parts of polyethylene terephthalate, 8-12 parts of composite antibacterial agent, 5-10 parts of antistatic agent, 3-7 parts of plasticizer, and 1-3 parts of antioxidant.

[0020] The present invention also provides surgical composite fibers prepared using the method for preparing surgical composite fibers.

[0021] The surgical suit composite fiber prepared in the above scheme can effectively kill bacteria and has good antibacterial and antistatic properties.

[0022] Compared with the prior art, the surgical wear composite fiber and its preparation method provided by the present invention have the following technical advantages: (1) The present invention uses polypropylene and polyethylene terephthalate as base materials to improve the toughness and chemical resistance of composite fibers and increase the number of medical sterilization treatments for surgical gowns. (2) The present invention uses organic nano antibacterial agent, modified nano silver powder and inulin to form a composite antibacterial agent, and utilizes the complementary advantages and synergistic effects of each component to achieve a broad-spectrum antibacterial effect; (3) The present invention uses a mixture of ionic polymer and graphene oxide as an antistatic agent to form a conductive network in the fiber, thereby improving the antistatic performance of the fiber. Attached Figure Description

[0023] Figure 1 Infrared spectrum of the organic nano-antibacterial agent prepared in Example 3. Detailed Implementation

[0024] The following will provide further details with reference to specific embodiments, but the present invention is not limited to these embodiments. Those skilled in the art can make various modifications based on the basic idea of ​​the present invention, but as long as they do not depart from the basic idea of ​​the present invention, they are all within the scope of the present invention. The raw materials described in this specific embodiment are all commercially available.

[0025] Preparation Example 1 The preparation method of the organic nano-antibacterial agent is as follows: 20g of nano-titanium dioxide powder and 6g of 3-chloropropionyl chloride are added to 400g of ethyl acetate. Under nitrogen protection, the mixture is heated to 45℃, sealed, and stirred for 6 hours to allow the hydroxyl groups on the surface of the nano-titanium dioxide to undergo an acylation reaction with 3-chloropropionyl chloride, introducing active chlorine groups. The mixture is then centrifuged and washed three times alternately with anhydrous ethanol and deionized water. It is then vacuum dried at 60℃ and 0.008MPa for 4 hours to obtain activated nano-titanium dioxide powder. 600g of a mixed solvent of anhydrous ethanol and dimethyl sulfoxide (volume ratio 3:1) is added to a reaction vessel, followed by 20g of activated titanium dioxide powder. The mixture is ultrasonically dispersed at 300W for 20 minutes, and then 14g of polyethyleneimine is added. The mixture is heated to 65℃ and stirred for 20 hours under nitrogen protection to allow the active chlorine groups on the surface of the activated nano-titanium dioxide powder to react with the 3-chloropropionyl chloride. The amino group in the enimine molecule undergoes a nucleophilic substitution reaction to achieve polyvinylimine grafting onto the surface of nano-titanium dioxide. After centrifugation, the intermediate is washed three times with anhydrous ethanol and vacuum-dried at 60°C and 0.008 MPa for 4 hours to obtain an antibacterial agent intermediate. 800 g of dioxane is added to a reaction vessel, and 20 g of the antibacterial agent intermediate is added under nitrogen protection. The mixture is ultrasonically dispersed at 300 W for 20 min, and 10 g of bromooctane is added. The mixture is heated to 55°C, sealed and stirred for 8 hours, cooled to 30°C, and 6 g of dimethyl sulfate is added. The mixture is sealed and stirred for 4 hours, centrifuged, washed four times successively with anhydrous ethanol and deionized water, and vacuum-dried at 60°C and 0.008 MPa for 4 hours to obtain an organic nano-antibacterial agent.

[0026] Preparation Example 2 The preparation method of the organic nano-antibacterial agent is as follows: 30g of nano-titanium dioxide powder and 10g of 3-chloropropionyl chloride are added to 500g of ethyl acetate. Under nitrogen protection, the mixture is heated to 55℃, sealed, and stirred for 8 hours to allow the hydroxyl groups on the surface of the nano-titanium dioxide to undergo an acylation reaction with 3-chloropropionyl chloride, introducing active chlorine groups. The mixture is then centrifuged and washed four times alternately with anhydrous ethanol and deionized water. It is then vacuum dried at 70℃ and 0.1MPa for 6 hours to obtain activated nano-titanium dioxide powder. 600g of a mixture of anhydrous ethanol and dimethyl sulfoxide (volume ratio 3:1) is added to a reaction vessel, followed by 30g of activated titanium dioxide powder. The mixture is ultrasonically dispersed at 400W for 30 minutes, and then 16g of polyethyleneimine is added. The mixture is heated to 75℃ and stirred for 24 hours under nitrogen protection to allow the active chlorine groups on the surface of the activated nano-titanium dioxide powder to react with the chlorine groups on the surface of the polyethyleneimine powder. The amino group in the enimine molecule undergoes a nucleophilic substitution reaction to achieve polyethyleneimine grafting onto the surface of nano-titanium dioxide. After centrifugation, the intermediate is washed three times with anhydrous ethanol and vacuum-dried at 70°C and 0.1 MPa for 6 hours to obtain an antibacterial agent intermediate. 800 g of dioxane is added to a reaction vessel, and 26 g of the antibacterial agent intermediate is added under nitrogen protection. The mixture is ultrasonically dispersed at 400 W for 30 min, and 14 g of bromooctane is added. The mixture is heated to 65°C, sealed and stirred for 10 hours, cooled to 35°C, and 10 g of dimethyl sulfate is added. The mixture is sealed and stirred for 6 hours, centrifuged, and washed four times successively with anhydrous ethanol and deionized water. After vacuum-drying at 70°C and 0.1 MPa for 6 hours, an organic nano-antibacterial agent is obtained.

[0027] Preparation Example 3 The preparation method of the organic nano-antibacterial agent is as follows: 27g of nano-titanium dioxide powder and 8g of 3-chloropropionyl chloride are added to 465g of ethyl acetate. Under nitrogen protection, the mixture is heated to 52℃, sealed, and stirred for 7h to allow the hydroxyl groups on the surface of the nano-titanium dioxide to undergo an acylation reaction with 3-chloropropionyl chloride, introducing active chlorine groups. The mixture is then centrifuged and washed four times alternately with anhydrous ethanol and deionized water. It is then vacuum dried at 65℃ and 0.05MPa for 5h to obtain activated nano-titanium dioxide powder. 600g of a mixed solvent of anhydrous ethanol and dimethyl sulfoxide (volume ratio 3:1) is added to a reaction vessel, followed by 27g of activated titanium dioxide powder. The mixture is ultrasonically dispersed at 355W for 25min, and then 15g of polyethyleneimine is added. The mixture is heated to 70℃ and stirred for 23h under nitrogen protection to allow the active chlorine groups on the surface of the activated nano-titanium dioxide powder to react with the chlorine groups on the surface of the polyethyleneimine powder. The amino group in the enimine molecule undergoes a nucleophilic substitution reaction to achieve polyethyleneimine grafting onto the surface of nano-titanium dioxide. After centrifugation, the intermediate is washed three times with anhydrous ethanol and vacuum-dried at 65°C and 0.05 MPa for 5 hours to obtain an antibacterial agent intermediate. 800 g of dioxane is added to a reaction vessel, and 23 g of the antibacterial agent intermediate is added under nitrogen protection. The mixture is ultrasonically dispersed at 355 W for 25 min, and 13 g of bromooctane is added. The mixture is heated to 60°C, sealed and stirred for 9 hours, cooled to 33°C, and 8 g of dimethyl sulfate is added. The mixture is sealed and stirred for 5 hours, centrifuged, washed four times successively with anhydrous ethanol and deionized water, and vacuum-dried at 65°C and 0.05 MPa for 5 hours to obtain an organic nano-antibacterial agent.

[0028] Preparation Example 4 The preparation method of the antistatic agent is as follows: 40g of terephthalic acid, 5g of sodium 5-sulfonate dimethyl isophthalate, 50g of ethylene glycol, 10g of N,N-dimethylformamide, and 10g of graphene oxide are added to a reaction vessel and stirred for 5 minutes. Then, 1g of tetrabutyl titanate and 3g of phosphoric acid are added and stirred for 5 minutes. Under nitrogen protection (nitrogen flow rate controlled at 50mL / min), the pressure of the reaction system is controlled at 0.1MPa, and the temperature is raised to 160℃. The reaction is stirred for 1 hour to allow some of the diacids and diols to undergo a preliminary esterification reaction. Then, the temperature is raised to 200℃ and the reaction is stirred for 3 hours to continue the esterification reaction, resulting in sulfonated polyester oligomer. The material was heated to 240℃, the pressure was reduced to 0.05MPa, and the mixture was stirred for 1 hour to remove residual water and a small amount of unreacted diol. The pressure was then reduced to 0.001MPa, and the mixture was stirred for 4 hours to carry out a polycondensation reaction, which further polymerized the sulfonated polyester oligomer. The temperature was then reduced to 180℃ and restored to normal pressure. The mixture was dried to obtain a crude antistatic agent. The crude product was crushed into particles with a diameter of 1mm and then added to anhydrous ethanol and stirred for 24 hours. This process was repeated 3 times. The mixture was then centrifuged, dried at 80℃ and 0.08MPa for 6 hours, and cooled to obtain the antistatic agent.

[0029] Preparation Example 5 The preparation method of the antistatic agent is as follows: 47g of terephthalic acid, 10g of sodium 5-sulfonate dimethyl isophthalate, 60g of ethylene glycol, 15g of N,N-dimethylformamide, and 15g of graphene oxide are added to a reaction vessel and stirred for 10 min. Then, 5g of tetrabutyl titanate and 8g of phosphoric acid are added and stirred for 10 min. Under nitrogen protection (nitrogen flow rate controlled at 100 mL / min), the pressure of the reaction system is controlled at 0.3 MPa, and the temperature is raised to 180℃. The reaction is stirred for 2 h to allow some of the diacid and diol to undergo a preliminary esterification reaction. Then, the temperature is raised to 220℃ and the reaction is stirred for 4 h to continue the esterification reaction, yielding sulfonated polyester low-carbon precipitate. The polymer was heated to 260℃, the pressure was reduced to 0.08MPa, and the reaction was stirred for 2 hours to remove residual water and a small amount of unreacted diol from the system. The pressure was then reduced to 0.005MPa, and the reaction was stirred for 6 hours to carry out a polycondensation reaction, which further polymerized the sulfonated polyester oligomer. The temperature was lowered to 200℃ and then restored to normal pressure. After drying, a crude antistatic agent was obtained. The crude product was crushed into particles with a particle size of 5mm and then added to anhydrous ethanol and stirred for 24 hours. This process was repeated 4 times. After centrifugation, the product was dried at 100℃ and 0.1MPa for 8 hours and then cooled to obtain the antistatic agent.

[0030] Preparation Example 6 The preparation method of the antistatic agent is as follows: 43g of terephthalic acid, 8g of sodium 5-sulfonate dimethyl isophthalate, 56g of ethylene glycol, 13g of N,N-dimethylformamide, and 13g of graphene oxide are added to a reaction vessel and stirred for 8 minutes. Then, 4g of tetrabutyl titanate and 5g of phosphoric acid are added and stirred for another 8 minutes. Under nitrogen protection (nitrogen flow rate controlled at 80mL / min), the pressure of the reaction system is controlled at 0.2MPa, and the temperature is raised to 170℃. The reaction is stirred for 1.5 hours to allow some of the dicarboxylic acid and diol to undergo a preliminary esterification reaction. Then, the temperature is raised to 210℃ and the reaction is stirred for 3.5 hours to continue the esterification reaction, yielding sulfonated polyester low-carbon precipitate. The polymer was heated to 250℃, the pressure was reduced to 0.07MPa, and the reaction was stirred for 1.5h to remove residual water and a small amount of unreacted diol from the system. The pressure was then reduced to 0.004MPa, and the reaction was stirred for 5h to carry out a polycondensation reaction, which further polymerized the sulfonated polyester oligomer. The temperature was lowered to 190℃ and then restored to normal pressure. After drying, a crude antistatic agent was obtained. The crude product was crushed into particles with a particle size of 4mm and then added to anhydrous ethanol for stirring and soaking for 24h. This process was repeated 4 times. After centrifugation, the product was dried at 95℃ and 0.09MPa for 7h and then cooled to obtain the antistatic agent.

[0031] Example 1 A method for preparing a composite fiber for surgical use includes: adding 5g of polypropylene, 50g of polyethylene terephthalate, 8g of a composite antibacterial agent, 5g of an antistatic agent, 3g of dibutyl phthalate, and 1g of antioxidant 1010 to a high-speed mixer and mixing at 80°C and 500 rpm for 30 minutes; then adding the mixture to a melt extruder and melting extruding at 300°C and a screw speed of 80 rpm to obtain a composite fiber spinning solution; and then melt spinning the solution through a spinneret with an orifice diameter of 0.2mm. The spinning temperature was 245℃, the spinning speed was 800m / min, and the nascent fibers after spinning were cooled in a cooling box with a cooling air temperature of 25℃ and a wind speed of 1.5m / s until room temperature was reached, thus obtaining nascent composite fibers. The nascent composite fibers were stretched at 80℃ with a stretch ratio of 2.5 times and a stretching speed of 50m / min, then heat-set at 120℃ for 10min, cooled, rinsed with warm water at 40℃ for 5min, and vacuum dried at 60℃ and a vacuum degree of 0.08MPa for 2h to obtain surgical wear composite fibers.

[0032] The composite antibacterial agent is composed of organic nano antibacterial agent, modified nano silver powder, and inulin in a mass ratio of 8:3:1; the organic nano antibacterial agent was prepared by Preparation Example 1; and the antistatic agent was prepared by Preparation Example 4.

[0033] The modified nano-silver powder was prepared as follows: 80g of anhydrous ethanol was added to a reaction vessel, and 10g of nano-silver powder was added under stirring. The mixture was ultrasonically dispersed at 300W for 20min. 5g of γ-methacryloyloxypropyltrimethoxysilane was added under stirring. The pH was adjusted to 4.0 with 1mol / L dilute acetic acid. The mixture was heated to 60℃ and stirred for 3h. After cooling, the mixture was centrifuged and the precipitate was washed three times with anhydrous ethanol. The precipitate was dried at 60℃ and 0.08MPa vacuum for 4h. After cooling, the mixture was ground to obtain the modified nano-silver powder.

[0034] Example 2 A method for preparing a composite fiber for surgical use includes: adding 10g of polypropylene, 40g of polyethylene terephthalate, 12g of a composite antibacterial agent, 10g of an antistatic agent, 7g of dibutyl phthalate, and 3g of antioxidant 1010 to a high-speed mixer and stirring at 90℃ and 600rpm for 40 minutes; then adding the mixture to a melt extruder and melting extruding at 320℃ and a screw speed of 100rpm to obtain a composite fiber spinning solution; and finally, melt spinning through a spinneret with an orifice diameter of 0.3 mm. The spun fibers were produced at a spinning temperature of 255℃ and a spinning speed of 1000m / min. The nascent fibers were then cooled in a cooling box at a temperature of 30℃ and a speed of 2m / s until room temperature was reached, yielding nascent composite fibers. The nascent composite fibers were stretched at 90℃ with a stretch ratio of 3 times and a stretching speed of 60m / min. They were then heat-set at 130℃ for 15 minutes, cooled, rinsed with warm water at 50℃ for 10 minutes, and vacuum-dried at 70℃ and a vacuum degree of 0.1MPa for 3 hours to obtain surgical wear composite fibers.

[0035] The composite antibacterial agent is composed of organic nano antibacterial agent, modified nano silver powder, and inulin in a mass ratio of 11:5:2; the organic nano antibacterial agent was prepared in Preparation Example 2; and the antistatic agent was prepared in Preparation Example 5.

[0036] The modified nano-silver powder was prepared as follows: 100g of anhydrous ethanol was added to a reaction vessel, and 10g of nano-silver powder was added under stirring. The mixture was ultrasonically dispersed at 400W for 30min. 8g of γ-methacryloyloxypropyltrimethoxysilane was added under stirring. The pH was adjusted to 5.0 with 2mol / L dilute acetic acid. The mixture was heated to 70℃ and stirred for 5h. After cooling, the mixture was centrifuged and the precipitate was washed four times with anhydrous ethanol. The precipitate was dried at 70℃ and 0.1MPa vacuum for 6h. After cooling, the mixture was ground to obtain the modified nano-silver powder.

[0037] Example 3 A method for preparing a composite fiber for surgical use includes: adding 8g of polypropylene, 46g of polyethylene terephthalate, 10g of a composite antibacterial agent, 8g of an antistatic agent, 6g of dibutyl phthalate, and 2g of antioxidant 1010 to a high-speed mixer and stirring at 85°C and 580 rpm for 35 minutes; then adding the mixture to a melt extruder and melting extruding at 310°C and a screw speed of 90 rpm to obtain a composite fiber spinning solution; and then melt spinning the solution through a spinneret with an orifice diameter of 0.2mm. The spinning temperature was 250℃, the spinning speed was 900m / min, and the nascent fibers after spinning were cooled in a cooling box with a cooling air temperature of 28℃ and a wind speed of 1.8m / s until room temperature was reached, thus obtaining nascent composite fibers. The nascent composite fibers were stretched at 85℃ with a stretch ratio of 2.8 times and a stretching speed of 55m / min, then heat-set at 125℃ for 13min, cooled, rinsed with warm water at 45℃ for 8min, and vacuum dried at 65℃ and a vacuum degree of 0.09MPa for 2.5h to obtain surgical wear composite fibers.

[0038] The composite antibacterial agent is composed of organic nano antibacterial agent, modified nano silver powder, and inulin in a mass ratio of 9:4:1; the organic nano antibacterial agent was prepared in Preparation Example 3; and the antistatic agent was prepared in Preparation Example 6.

[0039] The modified nano-silver powder was prepared as follows: 95g of anhydrous ethanol was added to a reaction vessel, and 10g of nano-silver powder was added under stirring. The mixture was ultrasonically dispersed at 350W for 25min. 7g of γ-methacryloyloxypropyltrimethoxysilane was added under stirring. The pH was adjusted to 4.5 with 1.5mol / L dilute acetic acid. The mixture was heated to 65℃ and stirred for 4h. After cooling, the mixture was centrifuged, and the precipitate was washed four times with anhydrous ethanol. The precipitate was dried at 65℃ and a vacuum of 0.09MPa for 5h. After cooling, the mixture was ground to obtain the modified nano-silver powder.

[0040] Comparative Example 1 The preparation method of the composite fiber described in this comparative example is similar to that in Example 3. The difference between this comparative example and Example 3 is that the composite antibacterial agent in this comparative example uses an equal amount of modified nano-silver powder instead of organic nano-antibacterial agent.

[0041] Comparative Example 2 The preparation method of the composite fiber described in this comparative example is similar to that in Example 3. The difference between this comparative example and Example 3 is that the composite antibacterial agent in this comparative example uses an equal amount of nano-silver powder instead of modified nano-silver powder.

[0042] Comparative Example 3 The preparation method of the composite fiber described in this comparative example is similar to that in Example 3. The difference between this comparative example and Example 3 is that all the composite antibacterial agents in this comparative example are organic nano antibacterial agents.

[0043] Comparative Example 4 The preparation method of the composite fiber described in this comparative example is similar to that in Example 3. The difference between this comparative example and Example 3 is that the antistatic agent in this comparative example is a mixture of polyethylene glycol (molecular weight 6000) and graphene oxide.

[0044] Comparative Example 5 The preparation method of the composite fiber described in this comparative example is similar to that in Example 3. The difference between this comparative example and Example 3 is as follows: The preparation method of the antistatic agent in this comparative example is as follows: 43g of terephthalic acid, 8g of sodium 5-sulfonate dimethyl isophthalate, 56g of ethylene glycol, and 13g of N,N-dimethylformamide are added to a reaction vessel and stirred for 8 minutes. Then, 4g of tetrabutyl titanate and 5g of phosphoric acid are added and stirred for 8 minutes. Under nitrogen protection (nitrogen flow rate controlled at 80mL / min), the pressure of the reaction system is controlled at 0.2MPa, and the temperature is raised to 170℃. The reaction is stirred for 1.5 hours to allow some of the dicarboxylic acid and diol to undergo a preliminary esterification reaction. Then, the temperature is raised to 210℃ and the reaction is stirred for 3.5 hours to continue the esterification reaction, obtaining sulfonated polyester oligomers. The temperature is then raised to 250℃ to reduce the temperature. The pressure was increased to 0.07 MPa, and the reaction was stirred for 1.5 h to remove residual water and a small amount of unreacted diol from the system. The pressure was then reduced to 0.004 MPa, and the reaction was stirred for 5 h to carry out a polycondensation reaction, allowing the sulfonated polyester oligomer to further polymerize. The temperature was lowered to 190 °C and then restored to normal pressure. 13 g of graphene oxide was added, stirred evenly, and dried to obtain a crude antistatic agent. The crude product was crushed into particles with a particle size of 4 mm and then added to anhydrous ethanol for stirring and soaking for 24 h. This process was repeated 4 times. The product was then centrifuged, dried at 95 °C and 0.09 MPa for 7 h, and cooled to obtain the antistatic agent.

[0045] Comparative Example 6 The preparation method of the composite fiber described in this comparative example is similar to that in Example 3. The difference between this comparative example and Example 3 is that graphene oxide was not added in the preparation method of the antistatic agent in this comparative example.

[0046] Test case Antibacterial performance test: The antibacterial properties of the composite fibers prepared in Examples 1-3 and Comparative Examples 1-6 were tested in accordance with GB / T 20944.3-2008. Antistatic performance test: The resistivity of the composite fibers prepared in Examples 1-3 and Comparative Examples 1-6 was tested in accordance with GB / T 14342-2015; Mechanical property testing: The composite fibers prepared in Examples 1-3 were tested for tensile strength and elongation at break in accordance with GB / T 14337-2022. The test results are shown in Table 1.

[0047] Table 1 Performance Test Results

[0048] As shown in Table 1, the surgical composite fiber prepared by this invention has good long-lasting antistatic, antibacterial, and mechanical properties, with the surgical composite fiber prepared in Example 3 showing the best effect. Compared with Example 3, the composite fiber prepared by using modified nano-silver powder instead of organic nano-antibacterial agent, nano-silver powder instead of modified nano-silver powder, and using only organic nano-antibacterial agents all resulted in varying degrees of reduction in the antibacterial rates of Escherichia coli and Staphylococcus aureus. This indicates that the organic nano-antibacterial agent, modified nano-silver powder, and inulin have a synergistic effect. Modifying nano-silver powder with a silane coupling agent can improve its dispersibility, thereby enhancing the antibacterial effect. Using a mixture of polyethylene glycol and graphene oxide as an antistatic agent and changing the way graphene oxide is added both lead to an increase in the resistivity of the composite fiber. This indicates that using a mixture of ionic polymers interspersed with graphene oxide as an antistatic agent can effectively reduce the resistivity of the composite fiber and improve the antistatic effect.

[0049] Furthermore, the present invention also conducted infrared spectroscopy tests on the organic nano-antibacterial agent prepared in Preparation Example 3, and the test results are as follows: Figure 1 As shown. By Figure 1 It can be seen that at 2869cm -1 The stretching vibration peak of CH in alkane appeared at 2346 cm⁻¹, which is caused by the introduction of alkyl groups by grafting polyethyleneimine onto nano-titanium dioxide after activation by 3-chloropropionyl chloride; -1 The absorption peak at 1398 cm⁻¹ is due to the formation of secondary ammonium salts from some of the imine nitrogen when polyethyleneimine is grafted onto the surface of nano-titanium dioxide; -1 The appearance of a CH bending vibration peak at the location confirms the presence of alkyl groups on the surface of the nano-titanium dioxide. Therefore, the nano-titanium dioxide was alkylated with octane bromide and dimethyl sulfate to obtain an alkylated polyethyleneimine-grafted nano-titanium dioxide antibacterial agent.

[0050] This specific embodiment is merely an explanation of the present invention and is not intended to limit the invention. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they are within the scope of the claims of the present invention.

Claims

1. A method for preparing a surgical surgical composite fiber, characterized in that, Specifically, polypropylene, polyethylene terephthalate, composite antibacterial agent, antistatic agent, plasticizer and antioxidant are mixed evenly, melt extruded to obtain composite fiber spinning solution, then melt spun through a spinneret, cooled and stretched, heat set, cooled, washed and dried to obtain surgical wear composite fiber; The composite antibacterial agent is composed of organic nano antibacterial agent, modified nano silver powder, and inulin in a mass ratio of (8-11):(3-5):(1-2).

2. The method for preparing the surgical surgical composite fiber according to claim 1, characterized in that, The preparation method of the organic nano-antibacterial agent is as follows: Nano-titanium dioxide powder and 3-chloropropionyl chloride are added to ethyl acetate, and the mixture is heated to 45-55℃ under nitrogen protection, sealed, and stirred for 6-8 hours. After centrifugation and washing, activated nano-titanium dioxide powder is obtained. Anhydrous ethanol and dimethyl sulfoxide mixed solvent are added to a reaction vessel, followed by the addition of activated titanium dioxide powder. The mixture is then ultrasonically dispersed, and polyethyleneimine is added. The mixture is heated to 65-75℃, stirred under nitrogen protection for 20-24 hours, centrifuged, washed, and dried to obtain an antibacterial agent intermediate. Dioxane is added to the reaction vessel, and the antibacterial agent intermediate is added under nitrogen protection. The mixture is ultrasonically dispersed, and bromooctane is added. The mixture is heated to 55-65℃, sealed, and stirred for 8-10 hours. The mixture is then cooled to 30-35℃, and dimethyl sulfate is added. The mixture is sealed and stirred for 4-6 hours, centrifuged, washed, and dried to obtain the organic nano-antibacterial agent.

3. The method for preparing the surgical surgical composite fiber according to claim 2, characterized in that, In the preparation method of the organic nano antibacterial agent, the mass ratio of ethyl acetate, nano titanium dioxide powder and 3-chloropropionyl chloride is (20-25):(1-1.5):(0.3-0.5); the volume ratio of anhydrous ethanol and dimethyl sulfoxide in the mixed solvent is 3:1, and the mass ratio of the mixed solvent of anhydrous ethanol and dimethyl sulfoxide, activated titanium dioxide powder and polyethyleneimine is 30:(1-1.5):(0.7-0.8); the mass ratio of dioxane, antibacterial agent intermediate, bromooctane and dimethyl sulfate is 40:(1-1.3):(0.5-0.7):(0.3-0.5).

4. The method for preparing the surgical surgical composite fiber according to claim 1, characterized in that, The modified nano-silver powder is prepared by adding anhydrous ethanol into a reaction vessel, adding nano-silver powder under stirring, dispersing it evenly by ultrasonication, adding γ-methacryloyloxypropyltrimethoxysilane under stirring, adjusting the pH value to 4.0-5.0, heating to 60-70℃, stirring and reacting for 3-5 hours, cooling, centrifuging, washing, drying, cooling, and grinding to obtain modified nano-silver powder.

5. The method for preparing the surgical surgical composite fiber according to claim 4, characterized in that, In the preparation method of modified nano-silver powder, the mass ratio of anhydrous ethanol, nano-silver powder, and γ-methacryloyloxypropyltrimethoxysilane is (8-10):1:(0.5-0.8).

6. The method for preparing the surgical surgical composite fiber according to claim 1, characterized in that, The antistatic agent is a mixture of ionic polymer and graphene oxide.

7. The method for preparing the surgical surgical composite fiber according to claim 6, characterized in that, The method for preparing the antistatic agent is as follows: Terephthalic acid, sodium 5-sulfonate dimethyl isophthalate, ethylene glycol, N,N-dimethylformamide, and graphene oxide are added to a reaction vessel and mixed evenly. Tetrabutyl titanate and phosphoric acid are added, and the mixture is stirred evenly. Under nitrogen protection, the pressure of the reaction system is controlled at 0.1-0.3 MPa. The temperature is raised to 160-180℃ and stirred for 1-2 hours. Then, the temperature is raised to 200-220℃ and stirred for 3-4 hours. The temperature is raised to 240-260℃, the pressure is reduced to 0.05-0.08 MPa, and the mixture is stirred for 1-2 hours. The pressure is reduced to 0.001-0.005 MPa and stirred for 4-6 hours. The temperature is lowered to 180-200℃ and then restored to normal pressure. The mixture is dried, added to anhydrous ethanol, stirred, and soaked for 24 hours. This process is repeated 3-4 times. The mixture is then dried, cooled, and ground to obtain the antistatic agent.

8. The method for preparing the surgical surgical composite fiber according to claim 7, characterized in that, The weight proportions of each component in the preparation method of the antistatic agent are as follows: 40-47 parts of terephthalic acid, 5-10 parts of sodium 5-sulfonate dimethyl isophthalate, 50-60 parts of ethylene glycol, 10-15 parts of N,N-dimethylformamide, 10-15 parts of graphene oxide, 1-5 parts of tetrabutyl titanate, and 3-8 parts of phosphoric acid.

9. The method for preparing the surgical surgical composite fiber according to claim 1, characterized in that, The plasticizer is dibutyl phthalate; the antioxidant is antioxidant 1010; the weight parts of each component in the preparation method of the surgical composite fiber are: 5-10 parts of polypropylene, 40-50 parts of polyethylene terephthalate, 8-12 parts of composite antibacterial agent, 5-10 parts of antistatic agent, 3-7 parts of plasticizer, and 1-3 parts of antioxidant.

10. A surgical suit made of composite fiber, characterized in that, It is prepared by the method for preparing surgical surgical composite fibers according to any one of claims 1-9.

Images