Long-acting antibacterial polyamide fiber and method for producing the same

Abstract

The present application relates to a long-acting antibacterial polyamide fiber and a preparation method thereof. The long-acting antibacterial polyamide fiber is composed of 4wt%-20wt% nylon-guanidine salt copolymer master batch and 80wt%-96wt% nylon, and the preparation method comprises the following steps: melt blending and reacting polystyrene-guanidine salt copolymer functional material obtained by melt blending and reacting polycyclic epoxy polystyrene synthesized by solution polymerization, suspension polymerization or bulk polymerization and guanidine salt polymer antibacterial agent; then melt blending with nylon to obtain nylon-guanidine salt copolymer master batch; and finally melt blending and spinning with nylon to obtain long-acting antibacterial polyamide fiber. By using the nylon-guanidine salt copolymer master batch of the present application, on the one hand, the antibacterial agent is chemically bonded to the polyamide matrix, ensuring the long-acting antibacterial property of the fiber; on the other hand, the antibacterial agent is enriched on the surface of the antibacterial polyamide fiber. The long-acting antibacterial polyamide fiber exhibits excellent antibacterial performance at a lower antibacterial agent dosage, thereby simultaneously maintaining good mechanical properties.

Description

Technical Field

[0001] This invention belongs to the field of functional fiber materials technology, specifically relating to a long-lasting antibacterial polyamide fiber, its preparation method, and its application. Background Technology

[0002] Polyamide or nylon fibers can be used in the manufacture of underwear, socks, sweatshirts, down jackets, windbreakers, protective clothing, fishing nets, curtain fabrics, carpets, conveyor belts, and transport belts. Because polyamide fibers themselves do not possess antibacterial properties, they can provide an environment for bacteria to survive and multiply under certain conditions, threatening human health. Antibacterial polyamide fibers can be prepared by introducing antibacterial components into the fibers or their surface through in-situ polymerization, melt spinning, and surface modification methods, thereby improving their overall performance and expanding their applications. Patents CN 105386147 A, CN 105332083 A, CN 111172609 A, CN112430864 A, and CN 113062005 A employ an in-situ polymerization method to prepare antibacterial polyamide chips by adding Ag@mesoporous zirconium phosphate antibacterial powder, copper oxide@mesoporous zirconium phosphate gel precursor, polyamine-supported nano-zinc oxide powder, antibacterial nano-metal powder encapsulated with Zr(HPO4)2 and polyfurfuryl alcohol, and powder with negative ion release antibacterial function to the polymer monomers. This method involves melt spinning. The in-situ polymerization method is technically challenging and difficult to scale up. Patent CN 108385202 A uses a method of first melt-blending long-chain carbon nylon with a silver ion-loaded antibacterial agent to prepare an antibacterial masterbatch, and then blending it with nylon chips for melt spinning to prepare colorfast antibacterial nylon fibers. Melt spinning is simple and easy to implement, but the silver ion antibacterial agent in the antibacterial fiber inhibits bacteria through dissolution, which may pose safety concerns. Patent CN117587541 A first reacts hydroxyethyl hexahydrotriazine with bisphenol A diglycidyl ether to obtain an antibacterial copolymer HE. Then, HE is reacted with a polyamide prepolymer to prepare an antibacterial polyamide. Finally, long-lasting antibacterial polyamide fibers are obtained through melt spinning. However, the amount of antibacterial agent added is large: when HE is added at 30% of the prepolymer mass, the antibacterial fiber prepared has an inhibition rate of only 92.8% against Escherichia coli and 94.5% against Staphylococcus aureus.

[0003] Guanidine salt polymers are highly efficient and broad-spectrum antibacterial agents with advantages such as good biocompatibility, low cost, non-toxicity, and good thermal stability. They have been widely used in pharmaceuticals, textiles, resins, medical devices, and water treatment. Their antibacterial mechanism involves the electrostatic attraction between the guanidine cationic groups on their own bodies and the anionic groups on the bacterial surface, attacking the bacteria, causing the bacterial membrane to collapse, and releasing the bacterial contents, thereby inhibiting bacterial growth. However, because the guanidine group is hydrophilic, most guanidine salt polymers are highly water-soluble. If directly applied to the antibacterial modification of polymer materials, there are drawbacks such as antibacterial agent dissolution and poor persistence. Therefore, a chemical reaction is needed to chemically bond the guanidine salt polymer antibacterial agent to the polymer matrix, thereby endowing the polymer material with long-lasting antibacterial properties. Summary of the Invention

[0004] To address the potential safety issues caused by antibacterial agent leaching, difficulties in preparation, or large amounts of antibacterial agent required for current antibacterial polyamide fibers, the present invention aims to provide a long-lasting antibacterial polyamide fiber that achieves long-lasting antibacterial effect by establishing chemical bonds between the guanidine salt polymer antibacterial agent and the polyamide through a blending reaction.

[0005] Another objective of this invention is to provide a method for preparing the above-mentioned long-lasting antibacterial polyamide fiber, which is simple and easy to implement, while enriching the guanidine salt polymer antibacterial agent on the surface of the fiber. On the one hand, this reduces the amount of antibacterial agent added, thereby reducing costs; on the other hand, it reduces the adverse effects of the antibacterial agent on the mechanical properties of the fiber, thus giving the antibacterial polyamide fiber good mechanical properties.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A long-lasting antibacterial polyamide fiber, comprising 4 wt% to 20 wt% of nylon-guanidine salt copolymer masterbatch and 80 wt% to 96 wt% of nylon; the nylon-guanidine salt copolymer masterbatch comprises a nylon-guanidine salt copolymer in which nylon and guanidine salt polymer are chemically bonded; the nylon is selected from nylon 6, nylon 66, and nylon 56; the nylon-guanidine salt copolymer is mainly composed of structural units shown in (structural formula A), (structural formula B), and (structural formula C).

[0008]

[0009] In the aforementioned structural formulas B and C, X is H or CH3 or a combination of both;

[0010] In the aforementioned structural formula B, Y is composed of the structural unit shown in (structural formula 1), (structural formula 2), or (structural formula 3);

[0011] In the aforementioned structural formula C, Z - For Cl - ,Br - HSO4 - HCO3 - H2PO4 - CH3COO - Or CH3(CH2) 16 COO - ;

[0012] In the aforementioned structural formula C, m is a natural number from 2 to 20;

[0013] In the aforementioned structural formula C, R1 is selected from the structure shown in (structural formula 4);

[0014] In the aforementioned structural formula C, R is H or the structure shown in (structural formula 5) or a combination of both.

[0015]

[0016] The present invention also provides a method for preparing the above-mentioned long-lasting antibacterial polyamide fiber, which includes the following steps:

[0017] (1) Styrene, functional monomers, initiators and chain transfer agents are added to a solvent, stirred and mixed evenly, and then heated to 50-85℃ for 9-12 hours. After cooling, the product is dropped into ethanol or methanol to precipitate. After filtration and drying, polyepoxy polystyrene is obtained.

[0018] Or (2) Styrene, functional monomer and initiator are stirred and mixed evenly, then added to an aqueous solution containing dispersant, stirring is started, the temperature is raised to 60-90℃ and reacted for 7-11 hours, and after cooling, cleaning and drying, polyepoxy polystyrene is obtained;

[0019] Or (3) Styrene, functional monomer and benzoyl peroxide initiator are stirred and mixed evenly, and then fed into the feed port of the twin-screw extruder. Under the condition that the temperature of the screw extruder is 80℃~160℃ in zones 1-16, the reaction is carried out for 6~30 minutes. After extrusion and cooling, polyepoxy polystyrene is obtained.

[0020] (4) After the polyepoxy polystyrene prepared in step (1), step (2) or step (3) is mixed with the guanidine salt polymer at a mass ratio of 7:3 to 9:1, it is added to a two-roll mill, a Hack internal mixer, a single screw extruder or a twin screw extruder and mixed at 140 to 200°C for 6 to 20 minutes. After cooling, the polystyrene-guanidine salt copolymer functional material is obtained.

[0021] (5) After mixing the polystyrene-guanidine salt copolymer functional material prepared in step (4) with nylon at a mass ratio of 3:17 to 3:7, add it to an open mill, Hack internal mixer, single screw extruder or twin screw extruder, and blend it at 5 to 30°C above the melting point of nylon for 6 to 30 minutes. After cooling, the nylon-guanidine salt copolymer masterbatch is obtained.

[0022] (6) After the nylon-guanidine salt copolymer masterbatch prepared in step (5) and nylon are thoroughly dried, they are mixed evenly at a mass ratio of 1:24 to 1:4 and then melt-spun to obtain long-lasting antibacterial polyamide fiber.

[0023] The method for preparing a long-lasting antibacterial polyamide fiber as described above, wherein the polyepoxy polystyrene is mainly composed of structural units shown in (structural formula A) and (structural formula D); in structural formula D, X is H or CH3 or a combination of both.

[0024]

[0025] The epoxy polystyrene has a molar percentage of epoxy groups of 3.5% to 10% and a number average molecular weight of 3,000 to 20,000.

[0026] Preferably, the molar percentage of epoxy groups in the polyepoxy polystyrene is 4.5% to 8.5%; and the number average molecular weight of the polyepoxy polystyrene is 4000 to 15000.

[0027] The method for preparing a long-lasting antibacterial polyamide fiber as described above, wherein the guanidine salt polymer has the structure shown in (structural formula E),

[0028]

[0029] In the guanidine salt polymer structure E, Z - For Cl - ,Br - HSO4 - HCO3 - H2PO4 - CH3COO - Or CH3(CH2) 16 COO - m is a natural number from 2 to 20; R1 is selected from the structure shown in (Structure 4); R is H or the structure shown in (Structure 5) or a combination of both;

[0030] Preferably, in the guanidine salt polymer structure E, Z - Selected from Cl - HCO3 -H2PO4 - Or CH3(CH2) 16 COO - R1 is the structure shown in (Structural Formula 6); R is the structure shown in (Structural Formula 7).

[0031]

[0032] In the preparation method of the long-lasting antibacterial polyamide fiber as described above, the functional monomer in step (1) is glycidyl methacrylate or glycidyl acrylate or a mixture of the two; the molar percentage of the functional monomer is based on the total amount of styrene and the functional monomer, and is 3.5% to 10%, preferably 5.0% to 8.0%.

[0033] In the preparation method of the long-lasting antibacterial polyamide fiber as described above, the total concentration of styrene and functional monomers in step (1) is based on the total mass of solvent, styrene and functional monomers, and is 10wt% to 40wt%, preferably 20wt% to 30wt%.

[0034] The preparation method of the long-lasting antibacterial polyamide fiber as described above, wherein the initiator in step (1) is one of azobisisobutyronitrile and benzoyl peroxide; the molar percentage of the initiator is based on the total amount of styrene and functional monomers, and is 1.0% to 3.0%;

[0035] The method for preparing a long-lasting antibacterial polyamide fiber as described above, wherein the chain transfer agent in step (1) is one of dodecyl mercaptoethanol, mercaptoethanol, mercaptopropanol, and isopropanol; the molar percentage of the chain transfer agent is based on the total amount of styrene and functional monomers, and is 0 to 1.2%.

[0036] In the preparation method of the long-lasting antibacterial polyamide fiber described above, the solvent in step (1) is one of toluene, xylene, tetrahydrofuran, and N,N-dimethylformamide.

[0037] In the preparation method of the long-lasting antibacterial polyamide fiber as described above, the functional monomer in step (2) is glycidyl methacrylate or glycidyl acrylate or a mixture of the two; the molar percentage of the functional monomer is based on the total amount of styrene and the functional monomer, and is 5.0% to 11.0%, preferably 7.0% to 10.0%.

[0038] In the preparation method of the long-lasting antibacterial polyamide fiber as described above, the initiator in step (2) is one of azobisisobutyronitrile and benzoyl peroxide; the molar percentage of the initiator is based on the total amount of styrene and functional monomers, and is 1.3% to 3.8%.

[0039] In the preparation method of the long-lasting antibacterial polyamide fiber described above, the ratio of the mass of water to the total mass of styrene and functional monomers in step (2) is 7:1 to 10:1;

[0040] In the preparation method of the long-lasting antibacterial polyamide fiber as described above, the dispersant in step (2) is one or a mixture of two of gelatin, polyvinyl alcohol, hydroxymethyl cellulose, hydroxyethyl cellulose, and sodium alginate; the mass percentage of the dispersant is based on the mass of water and is 0.2wt% to 0.5wt%.

[0041] In the preparation method of the long-lasting antibacterial polyamide fiber as described above, the functional monomer in step (3) is one or a mixture of glycidyl methacrylate and glycidyl acrylate; the molar percentage of the functional monomer is based on the total amount of styrene and the functional monomer, and is 3.5% to 10%, preferably 6.0% to 9.0%.

[0042] In the preparation method of the long-lasting antibacterial polyamide fiber described above, the molar percentage of the initiator in step (3) is based on the total amount of styrene and functional monomers, and is 1.0% to 5.0%.

[0043] In the preparation method of the long-lasting antibacterial polyamide fiber as described above, the polyepoxy polystyrene and the guanidine salt polymer in step (4) are mixed at a mass ratio of 4:1 to 17:3.

[0044] In the preparation method of the long-lasting antibacterial polyamide fiber as described above, the blending reaction temperature in step (4) is 150-180℃; and the blending reaction time is 6-15 minutes.

[0045] The preparation method of the long-lasting antibacterial polyamide fiber described above includes a polystyrene-guanidine salt copolymer in step (4); the polystyrene-guanidine salt copolymer is mainly composed of structural units shown in (structural formula A), (structural formula C) and (structural formula D).

[0046] In the preparation method of the long-lasting antibacterial polyamide fiber as described above, the polystyrene-guanidine salt copolymer functional material in step (5) is mixed with the nylon at a mass ratio of 1:4 to 1:3;

[0047] In the preparation method of the long-lasting antibacterial polyamide fiber described above, the blending reaction time in step (5) is 6 to 15 minutes.

[0048] In the preparation method of the long-lasting antibacterial polyamide fiber as described above, the nylon-guanidine salt copolymer masterbatch and nylon in step (6) are mixed at a mass ratio of 1:24 to 1:9;

[0049] In the above-described method for preparing a long-lasting antibacterial polyamide fiber, the melt spinning in step (6) is carried out at a temperature of 250–305°C, a spinning speed of 800–1500 m / min, a spinneret aperture of 0.2–0.5 mm, a stretching temperature of 60–120°C, and a stretching ratio of 3–4 times.

[0050] The preparation method of the long-lasting antibacterial polyamide fiber described above, wherein the antibacterial polyamide fiber in step (6) has a breaking strength of 3.5 to 5.8 cN / dtex and a breaking elongation of 10% to 50%, and has an antibacterial effect of more than 99.99% against Escherichia coli, Staphylococcus aureus and Candida albicans. After the fiber is washed 50 times, the antibacterial effect against Escherichia coli, Staphylococcus aureus and Candida albicans can still reach more than 99%, and it has good water resistance and high antibacterial properties.

[0051] The method for preparing a long-lasting antibacterial polyamide fiber as described above, wherein the antibacterial polyamide fiber described in step (6) can be applied to home textile products such as clothing, protective clothing, bed sheets, socks, and carpets.

[0052] The above-mentioned technical solution adopted in this invention involves chemically bonding a guanidine salt polymer antibacterial agent and nylon molecules to the molecular chain of a styrene copolymer through a blending reaction, thereby obtaining an antibacterial masterbatch containing nylon-guanidine salt copolymer mainly composed of structural units shown in (structural formula A), (structural formula B), and (structural formula C), i.e., a nylon-guanidine salt copolymer masterbatch; and in the fibers obtained by melt spinning the nylon-guanidine salt copolymer masterbatch and nylon, the guanidine salt polymer antibacterial agent is enriched on the fiber surface.

[0053] The positive and beneficial effects of this invention are as follows:

[0054] (1) The method for preparing antibacterial polyamide fiber provided by the present invention enriches the antibacterial agent on the fiber surface, and the antibacterial fiber exhibits good antibacterial activity at a low amount of antibacterial agent added.

[0055] (2) The antibacterial polyamide fiber provided by the present invention has a low content of antibacterial agent and good mechanical properties.

[0056] (3) The antibacterial polyamide fiber provided by the present invention has a chemical bond between the antibacterial agent and the nylon matrix, and the antibacterial properties of the antibacterial fiber are long-lasting and stable, and there is no safety problem of antibacterial agent leaching.

[0057] (4) The method for preparing antibacterial polyamide fiber provided by the present invention is simple and easy to scale up. Attached Figure Description

[0058] Figure 1 The image shows a scanning electron microscope (SEM) image of the cross-section of the antibacterial nylon 6-f9 nascent fiber obtained in Example 50 of this invention, along with its line scan chlorine element distribution map. Detailed Implementation

[0059] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0060] The testing standards / methods used in this invention are as follows:

[0061] The number-average molecular weight of the polyepoxy polystyrene synthesized in Examples 1 to 20 was determined by gel permeation chromatography (GPC) using tetrahydrofuran as solvent. The epoxy value of the polyepoxy polystyrene synthesized in Examples 1 to 20 was determined by hydrochloric acid-acetone method according to GB / T 1677-2008. Combined with the number-average molecular weight determined by GPC, the molar percentage of epoxy groups in the polyepoxy polystyrene was calculated.

[0062] The dispersion phenomenon in ethyl acetate (a good solvent for polystyrene) was used to determine whether the polystyrene-guanidine salt copolymer functional materials prepared in Examples 21 to 45 contained cross-linked structures: 1 g of polystyrene-guanidine salt copolymer functional material was weighed and placed in 50 mL of ethyl acetate. After sealing, it was ultrasonically dispersed, and the dispersion phenomenon of the functional material was observed. If the polystyrene-guanidine salt copolymer functional material could be completely ultrasonically dispersed in ethyl acetate, it indicated that the functional material did not contain cross-linked structures.

[0063] The grafting rate of guanidine salt polymer in the polystyrene-guanidine salt copolymer functional materials prepared in Examples 21 to 45 was determined by ultraviolet spectrophotometry: A series of aqueous solutions of guanidine salt polymer were prepared, and the absorbance of the solution at 196 nm was measured. Then, a standard curve was plotted. The polystyrene-guanidine salt copolymer functional material was ground into powder under infrared lamp baking. 400 mg of powder was accurately weighed and added to an Erlenmeyer flask. 200 mL of deionized water was added, and the flask was sealed and placed in a constant temperature shaking incubator. The mixture was shaken at 25–40 °C for 4 h. After removal, the mixture was equilibrated at 25 °C for 24 h. After centrifugation (8000 rpm, 5–10 min), the supernatant was collected and diluted with deionized water to the concentration range of the standard curve. The absorbance of the diluted solution at 196 nm was measured using an ultraviolet spectrophotometer. The mass of dissolved guanidine salt polymer was calculated according to the standard curve, and the grafting rate of guanidine salt polymer in the polystyrene-guanidine salt copolymer functional material was thus calculated.

[0064] According to GB / T 14344-2008 Test Method for Tensile Properties of Chemical Fiber Filaments, the breaking strength and breaking elongation of polyamide fibers spun in Examples 50 to 53 and Comparative Examples 4 to 7 were determined.

[0065] According to GB / T12490-2014 Textiles - Tests for Color Fastness to Domestic and Commercial Washing, the antibacterial polyamide fibers spun in Examples 50 to 53 were subjected to water washing treatment:

[0066] According to GB / T20944.3-2008 Evaluation of antimicrobial properties of textiles - Part 3: Vibration method, the inhibition rates of antimicrobial polyamide fibers spun in Control Examples 5 to 7 and antimicrobial polyamide fibers spun in Examples 50 to 53 against Escherichia coli, Staphylococcus aureus and Candida albicans before and after water washing were determined.

[0067] The morphology and composition of the cross-section of the antibacterial nylon 6-f9 nascent fibers obtained in Example 50, which were broken in liquid nitrogen, were observed and scanned using scanning electron microscopy.

[0068] Examples 1-20 are examples of the synthesis of polyepoxy polystyrene.

[0069] Example 1: Synthesis of polyepoxy polystyrene

[0070] 83.97 g styrene, 6.03 g glycidyl methacrylate, 2.09 g azobisisobutyronitrile, 0.86 g dodecanethiol, and 210 g toluene were sequentially added to a 500 mL three-necked reaction flask equipped with a reflux condenser and stirred until dissolved. Nitrogen gas was introduced into the apparatus for 10 min. The temperature was raised to 75 °C and the reaction was maintained at this temperature for 10 h. After the reaction was stopped, the reaction solution was cooled to room temperature and then added dropwise to excess ethanol. The mixture was filtered, and the precipitate was collected. The precipitate was washed with ethanol and dried under vacuum at 60 °C for 12 h to obtain the epoxy polystyrene product, denoted as SG-1.

[0071] Example 2: Synthesis of polyepoxy polystyrene

[0072] 130.19 g styrene, 5.81 g glycidyl acrylate, 2.13 g azobisisobutyronitrile, 0.39 g isopropanol, and 204 g tetrahydrofuran were sequentially added to a 500 mL three-necked reaction flask equipped with a condenser and stirred until dissolved. Nitrogen gas was introduced into the apparatus for 10 min. The temperature was raised to 50 °C and the reaction was maintained at that temperature for 12 h. After the reaction was stopped, the reaction solution was cooled to room temperature and added dropwise to excess methanol. The mixture was filtered, and the precipitate was collected. The precipitate was washed with methanol and dried under vacuum at 60 °C for 12 h to obtain the epoxy polystyrene product, denoted as SG-2.

[0073] Example 3: Synthesis of polyepoxy polystyrene

[0074] 64.36 g styrene, 7.64 g glycidyl methacrylate, 4.07 g benzoyl peroxide, 0.50 g mercaptopropanol, and 288 g N,N-dimethylformamide were sequentially added to a 500 mL three-necked reaction flask equipped with a condenser and stirred until dissolved. Nitrogen gas was introduced into the apparatus for 10 min. The temperature was raised to 85 °C and the reaction was maintained at this temperature for 9 h. After the reaction was stopped, the reaction solution was cooled to room temperature and added dropwise to excess ethanol. The mixture was filtered, and the precipitate was collected. The precipitate was washed with ethanol and dried under vacuum at 60 °C for 12 h to obtain the epoxy polystyrene product, denoted as SG-3.

[0075] Example 4: Synthesis of polyepoxy polystyrene

[0076] 82.79 g styrene, 7.21 g glycidyl methacrylate, 2.05 g benzoyl peroxide, 0.79 g mercaptoethanol, and 270 g xylene were sequentially added to a 500 mL three-necked reaction flask equipped with a condenser and stirred until dissolved. Nitrogen gas was introduced into the apparatus for 10 min. The temperature was raised to 85 °C and the reaction was maintained at this temperature for 9 h. After the reaction was stopped, the reaction solution was cooled to room temperature and then added dropwise to excess ethanol. The mixture was filtered, and the precipitate was collected. The precipitate was washed with ethanol and dried under vacuum at 60 °C for 12 h to obtain the epoxy polystyrene product, denoted as SG-4.

[0077] Example 5: Synthesis of polyepoxy polystyrene

[0078] 31.67 g styrene, 4.33 g glycidyl acrylate, 1.66 g azobisisobutyronitrile, and 324 g N,N-dimethylformamide were sequentially added to a 500 mL three-necked reaction flask equipped with a condenser and stirred until dissolved. Nitrogen gas was introduced into the apparatus for 10 min. The temperature was raised to 70 °C and the reaction was maintained at this temperature for 10 h. After the reaction was stopped, the reaction solution was cooled to room temperature and then added dropwise to excess ethanol. The mixture was filtered, and the precipitate was collected. The precipitate was washed with ethanol and dried under vacuum at 60 °C for 12 h to obtain the epoxy polystyrene product, denoted as SG-5.

[0079] Example 6: Synthesis of polyepoxy polystyrene

[0080] 82.79 g styrene, 7.21 g glycidyl methacrylate, 2.78 g azobisisobutyronitrile, and 270 g tetrahydrofuran were sequentially added to a 500 mL three-necked reaction flask equipped with a condenser and stirred until dissolved. Nitrogen gas was introduced into the apparatus for 10 min. The temperature was raised to 75 °C and the reaction was maintained at this temperature for 10 h. After the reaction was stopped, the reaction solution was cooled to room temperature and then added dropwise to excess ethanol. The mixture was filtered, and the precipitate was collected. The precipitate was washed with ethanol and dried under vacuum at 60 °C for 12 h to obtain a polyepoxy polystyrene compound, denoted as SG-6.

[0081] Table 1 lists the epoxy group content and number-average molecular weight data of the polyepoxy polystyrene obtained in Examples 1-6.

[0082] Table 1. Epoxy group content and number-average molecular weight data of polyoxyethylene polystyrene synthesized by solution polymerization.

[0083]

[0084] Number average molecular weight; the amount of functional monomer is based on the total amount of functional monomer and styrene; the total monomer concentration is the total mass percentage of functional monomer and styrene, based on the total mass of solvent, functional monomer, and styrene; the amount of initiator is based on the total amount of functional monomer and styrene; the amount of chain transfer agent is based on the total amount of functional monomer and styrene; GMA - glycidyl methacrylate; GA - glycidyl acrylate; AIBN - azobisisobutyronitrile; BPO - benzoyl peroxide; DT - dodecanethiol; IPA - isopropanol; MP - mercaptopropanol; ME - mercaptoethanol; THF - tetrahydrofuran; DMF - N,N-dimethylformamide; DMB - xylene; TL - toluene

[0085] Example 7: Synthesis of polyepoxy polystyrene

[0086] 150g of a 4wt% polyvinyl alcohol aqueous solution and 1050g of deionized water were added to a 2L jacketed glass reactor equipped with a serpentine condenser and mechanically stirred (at a speed of 350rpm) for at least 5 minutes. 159.94g of styrene monomer and 9.29g of azobisisobutyronitrile initiator were added to a 250mL beaker and stirred until the initiator was completely dissolved. Then, 11.49g of glycidyl methacrylate was added and stirred again until homogeneous. This mixture was then added to the reactor. After stirring for 0.5 hours, 75°C circulating hot water was introduced into the reactor jacket and the reaction was carried out at a constant temperature for 9 hours. After cooling to room temperature, the polymer particles were collected and washed successively with hot water and ethanol. After vacuum drying at 60°C for 12 hours, the polyepoxy polystyrene product was obtained, designated SG-7.

[0087] Example 8: Synthesis of polyepoxy polystyrene

[0088] 60g of a 4wt% gelatin aqueous solution and 1140g of deionized water were added to a 2L jacketed glass reactor equipped with a serpentine condenser and mechanically stirred (at 350rpm) for at least 5 minutes. 148.80g of styrene monomer and 10.02g of azobisisobutyronitrile initiator were added to a 250mL beaker and stirred until the initiator was completely dissolved. Then, 22.63g of glycidyl acrylate was added and stirred again until homogeneous. The mixture was then added to the reactor. After stirring for 0.5 hours, circulating hot water at 60℃ was introduced into the reactor jacket and the reaction was carried out at a constant temperature for 11 hours. After cooling to room temperature, the polymer particles were collected and washed successively with hot water and ethanol. After vacuum drying at 60℃ for 12 hours, the polyepoxy polystyrene product was obtained, denoted as SG-8.

[0089] Example 9: Synthesis of polyepoxy polystyrene

[0090] 90g of a 4wt% sodium alginate aqueous solution and 1110g of deionized water were added to a 2L jacketed glass reactor equipped with a serpentine condenser and mechanically stirred (at 350rpm) for at least 5 minutes. 119.18g of styrene monomer and 6.63g of benzoyl peroxide initiator were added to a 250mL beaker and stirred until the initiator was completely dissolved. Then, 14.15g of glycidyl methacrylate was added and stirred again until homogeneous. This mixture was then added to the reactor. After stirring for 0.5 hours, circulating hot water at 85℃ was introduced into the reactor jacket, and the reaction was carried out at a constant temperature for 8 hours. After cooling to room temperature, the polymer particles were collected, washed successively with hot water and ethanol, and dried under vacuum at 60℃ for 12 hours to obtain the epoxy polystyrene product, designated SG-9.

[0091] Example 10: Synthesis of polyepoxy polystyrene

[0092] 120g of a 4wt% aqueous solution of hydroxymethyl cellulose and 1080g of deionized water were added to a 2L jacketed glass reactor equipped with a serpentine condenser and mechanically stirred (at 350rpm) for at least 5 minutes. 110.38g of styrene monomer and 6.01g of benzoyl peroxide initiator were added to a 250mL beaker and stirred until the initiator was completely dissolved. Then, 9.62g of glycidyl methacrylate was added and stirred again until homogeneous. The mixture was then added to the reactor. After stirring for 0.5 hours, circulating hot water at 90℃ was introduced into the reactor jacket and the reaction was carried out at a constant temperature for 7 hours. After cooling to room temperature, the polymer particles were collected and washed successively with hot water and ethanol. After vacuum drying at 60℃ for 12 hours, the polyepoxy polystyrene product was obtained, denoted as SG-10.

[0093] Example 11: Synthesis of polyepoxy polystyrene

[0094] 120g of a 4wt% hydroxyethyl cellulose aqueous solution and 1080g of deionized water were added to a 2L jacketed glass reactor equipped with a serpentine condenser and mechanically stirred (at 350rpm) for at least 5 minutes. 151.04g of styrene monomer and 9.94g of azobisisobutyronitrile initiator were added to a 250mL beaker and stirred until the initiator was completely dissolved. Then, 20.39g of glycidyl methacrylate was added and stirred again until homogeneous. This mixture was then added to the reactor. After stirring for 0.5 hours, 70℃ circulating hot water was introduced into the reactor jacket and the reaction was carried out at a constant temperature for 10 hours. After cooling to room temperature, the polymer particles were collected and washed successively with hot water and ethanol. After vacuum drying at 60℃ for 12 hours, the polyepoxy polystyrene product was obtained, designated SG-11.

[0095] Example 12: Synthesis of polyepoxy polystyrene

[0096] 120g of a 4wt% polyvinyl alcohol aqueous solution and 1080g of deionized water were added to a 2L jacketed glass reactor equipped with a serpentine condenser and mechanically stirred (at a speed of 350rpm) for at least 5 minutes. 130.25g of styrene monomer and 10.10g of benzoyl peroxide initiator were added to a 250mL beaker and stirred until the initiator was completely dissolved. Then, 19.75g of glycidyl methacrylate was added and stirred again until homogeneous. This mixture was then added to the reactor. After stirring for 0.5 hours, circulating hot water at 80℃ was introduced into the reactor jacket, and the reaction was carried out at a constant temperature for 9 hours. After cooling to room temperature, the polymer particles were collected and washed successively with hot water and ethanol. After vacuum drying at 60℃ for 12 hours, the polyepoxy polystyrene product was obtained, designated SG-12.

[0097] Example 13: Synthesis of polyepoxy polystyrene

[0098] 120g of a 4wt% polyvinyl alcohol aqueous solution and 1080g of deionized water were added to a 2L jacketed glass reactor equipped with a serpentine condenser and mechanically stirred (at 350rpm) for at least 5 minutes. 126.46g of styrene monomer and 10.03g of benzoyl peroxide initiator were added to a 250mL beaker and stirred until the initiator was completely dissolved. Then, 23.54g of glycidyl methacrylate was added and stirred again until homogeneous. This mixture was then added to the reactor. After stirring for 0.5 hours, circulating hot water at 85℃ was introduced into the reactor jacket, and the reaction was carried out at a constant temperature for 9 hours. After cooling to room temperature, the polymer particles were collected and washed successively with hot water and ethanol. After vacuum drying at 60℃ for 12 hours, the polyepoxy polystyrene product was obtained, designated SG-13.

[0099] Example 14: Synthesis of polyepoxy polystyrene

[0100] 120g of a 4wt% polyvinyl alcohol aqueous solution and 1080g of deionized water were added to a 2L jacketed glass reactor equipped with a serpentine condenser and mechanically stirred (at 350rpm) for at least 5 minutes. 136.03g of styrene monomer and 4.42g of benzoyl peroxide initiator were added to a 250mL beaker and stirred until the initiator was completely dissolved. Then, 13.97g of glycidyl methacrylate was added and stirred again until homogeneous. This mixture was then added to the reactor. After stirring for 0.5 hours, 70℃ circulating hot water was introduced into the reactor jacket and the reaction was carried out at a constant temperature for 10 hours. After cooling to room temperature, the polymer particles were collected and washed successively with hot water and ethanol. After vacuum drying at 60℃ for 12 hours, the polyepoxy polystyrene product was obtained, designated SG-14.

[0101] Table 2 lists the epoxy group content and number-average molecular weight data of the polyepoxy polystyrene obtained in Examples 7-14.

[0102] Table 2. Epoxy group content and number-average molecular weight data of polyoxyethylene polystyrene synthesized by suspension polymerization.

[0103]

[0104] Number average molecular weight; the amount of functional monomer is based on the total amount of functional monomer and styrene; the water-oil ratio is the ratio of the mass of water to the total mass of styrene and functional monomer; the amount of initiator is based on the total amount of functional monomer and styrene; the amount of dispersant is based on the mass of water; GMA - glycidyl methacrylate; GA - glycidyl acrylate; AIBN - azobisisobutyronitrile; BPO - benzoyl peroxide; PVA - polyvinyl alcohol; GEL - gelatin; HMC - hydroxymethyl cellulose; HEC - hydroxyethyl cellulose; SA - sodium alginate.

[0105] Example 15: Synthesis of polyepoxy polystyrene

[0106] 228.4 g of benzoyl peroxide was dissolved in 1866.0 g of styrene and then mixed evenly with 134.0 g of methyl methacrylate. The mixture was fed into the feed port of a twin-screw extruder at a speed of 5 kg / h. The reaction was extruded at temperatures of 80℃, 85℃, 90℃, 95℃, 100℃, 110℃, 120℃, 130℃, 130℃, 135℃, 135℃, 135℃, 150℃, 150℃, and 160℃ in zones 1-16 of the screw extruder, and at a speed of 50 rpm. After cooling, the polyepoxy polystyrene product was obtained, denoted as SG-15.

[0107] Example 16: Synthesis of polyepoxy polystyrene

[0108] 184.6 g of benzoyl peroxide was dissolved in 1914.6 g of styrene and then mixed evenly with 85.4 g of methyl acrylate. The mixture was fed into the feed port of a twin-screw extruder at a speed of 5 kg / h. The reaction was extruded at temperatures of 80℃, 85℃, 90℃, 95℃, 100℃, 110℃, 120℃, 130℃, 130℃, 135℃, 135℃, 135℃, 135℃, 150℃, 150℃, and 160℃ in zones 1-16 of the screw extruder, with a rotation speed of 50 rpm. After cooling, the polyepoxy polystyrene product was obtained, denoted as SG-16.

[0109] Example 17: Synthesis of polyepoxy polystyrene

[0110] 135.6 g of benzoyl peroxide was dissolved in 1787.8 g of styrene, and then mixed evenly with 212.2 g of methyl methacrylate. The mixture was fed into the feed port of a twin-screw extruder at a speed of 5 kg / h. The reaction was extruded at temperatures of 80℃, 85℃, 90℃, 95℃, 100℃, 110℃, 120℃, 130℃, 130℃, 135℃, 135℃, 135℃, 150℃, 150℃, and 160℃ in zones 1-16 of the screw extruder, and at a speed of 50 rpm. After cooling, the polyepoxy polystyrene product was obtained, denoted as SG-17.

[0111] Example 18: Synthesis of polyepoxy polystyrene

[0112] 91.0 g of benzoyl peroxide was dissolved in 1839.7 g of styrene and then mixed evenly with 160.3 g of methyl methacrylate. The mixture was fed into the feed port of a twin-screw extruder at a speed of 5 kg / h. The reaction was extruded at temperatures of 80℃, 85℃, 90℃, 95℃, 100℃, 110℃, 120℃, 130℃, 130℃, 135℃, 135℃, 135℃, 135℃, 150℃, 150℃, and 160℃ in zones 1-16 of the screw extruder, and at a speed of 50 rpm. After cooling, the polyepoxy polystyrene product was obtained, denoted as SG-18.

[0113] Example 19: Synthesis of polyepoxy polystyrene

[0114] 44.9 g of benzoyl peroxide was dissolved in 1736.6 g of styrene and then mixed evenly with 263.4 g of methyl methacrylate. The mixture was fed into the feed port of a twin-screw extruder at a speed of 5 kg / h. The reaction was extruded at temperatures of 80℃, 85℃, 90℃, 95℃, 100℃, 110℃, 120℃, 130℃, 130℃, 135℃, 135℃, 135℃, 135℃, 150℃, 150℃, and 160℃, respectively, and at a speed of 50 rpm. After cooling, the polyepoxy polystyrene product was obtained, denoted as SG-19.

[0115] Example 20: Synthesis of polyepoxy polystyrene

[0116] 135.1g of benzoyl peroxide was dissolved in 1762.1g of styrene and then mixed evenly with 237.9g ​​of methyl methacrylate. The mixture was fed into the feed port of a twin-screw extruder at a rate of 5kg / h. The reaction was extruded at temperatures of 80℃, 85℃, 90℃, 95℃, 100℃, 110℃, 120℃, 130℃, 130℃, 135℃, 135℃, 135℃, 135℃, 150℃, 150℃, and 160℃, respectively, at a speed of 50rpm. After cooling, the polyepoxy polystyrene product was obtained, denoted as SG-20.

[0117] Table 3 lists the epoxy group content and number-average molecular weight data of the polyepoxy polystyrene obtained in Examples 15-20.

[0118] Table 3. Epoxy group content and number-average molecular weight data of polyoxyethylene polystyrene synthesized by bulk polymerization.

[0119] Number average molecular weight; the amount of functional monomer is based on the total amount of functional monomer and styrene; the amount of initiator is based on the total amount of functional monomer and styrene; GMA - glycidyl methacrylate; GA - glycidyl acrylate; BPO - benzoyl peroxide.

[0120] Using dodecylamine, n-octylamine, hexamethylenediamine, pentanediamine, and guanidine hydrochloride as raw materials, four guanidine salt polymers were synthesized by melt condensation polymerization. These include dodecylamine-terminated polyhexamethylene guanidine hydrochloride (denoted as PHMG-L, corresponding to the structure in formula (E), where Z... - For Cl - R1 is R is n-Octylamine-terminated polyhexamethylene guanidine hydrochloride (denoted as PHMG-O, corresponding to the structure in formula (E), Z) - For Cl - R1 is R is Polyhexamethylene guanidine hydrochloride (denoted as PHMG, corresponding to the structure in (E), Z) - For Cl - R1 is R is H), dodecylamine-terminated polypentamethylene guanidine hydrochloride (denoted as PPMG-L, corresponding to the structure in (E), Z - For Cl - R1 is R is The polymers were used in the preparation of polystyrene-guanidine salt copolymer functional materials in Examples 21 to 45, and in the preparation of antibacterial nylon 6 masterbatches in Comparative Examples 1 to 3. The number-average molecular weights of the guanidine salt polymers PHMG-L, PHMG-O, PHMG, and PPMG-L were determined by matrix-assisted laser desorption / ionization time-of-flight mass spectrometry to be 731, 606, 956, and 696, respectively.

[0121] Examples 21-45 are examples of the preparation of polystyrene-guanidine salt copolymer functional materials.

[0122] Example 21: Preparation of functional polystyrene-guanidine salt copolymer

[0123] 24g of the epoxy polystyrene SG-16 prepared in Example 16 and 6g of PHMG were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 170°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, denoted as PSGP-1.

[0124] Example 22: Preparation of functional materials of polystyrene-guanidine salt copolymer

[0125] 24g of the epoxy polystyrene SG-2 prepared in Example 2 and 6g of PHMG were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 170°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, denoted as PSGP-2.

[0126] Example 23: Preparation of functional materials of polystyrene-guanidine salt copolymer

[0127] 24g of the epoxy polystyrene SG-10 prepared in Example 10 and 6g of PHMG were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 170°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, denoted as PSGP-3.

[0128] Example 24: Preparation of polystyrene-guanidine salt copolymer functional materials

[0129] 24g of the epoxy polystyrene SG-18 prepared in Example 18 and 6g of PHMG were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 170°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, denoted as PSGP-4.

[0130] Example 25: Preparation of functional materials of polystyrene-guanidine salt copolymer

[0131] 24g of the epoxy polystyrene SG-17 prepared in Example 17 and 6g of PHMG were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 170°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, denoted as PSGP-5.

[0132] Example 26: Preparation of functional polystyrene-guanidine salt copolymer

[0133] 24g of the epoxy polystyrene SG-3 prepared in Example 19 and 6g of PHMG were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 170°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, denoted as PSGP-6.

[0134] Example 27: Preparation of functional materials of polystyrene-guanidine salt copolymer

[0135] 24g of the epoxy polystyrene SG-8 prepared in Example 8 and 6g of PHMG were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 170°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, denoted as PSGP-7.

[0136] Example 28: Preparation of functional materials of polystyrene-guanidine salt copolymer

[0137] 24g of the epoxy polystyrene SG-13 prepared in Example 13 and 6g of PHMG were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 170°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, denoted as PSGP-8.

[0138] Example 29: Preparation of polystyrene-guanidine salt copolymer functional materials

[0139] 24g of the epoxy polystyrene SG-14 prepared in Example 14 and 6g of PHMG were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 170°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, denoted as PSGP-9.

[0140] As can be seen from the data in Examples 21-27 of Table 4, the grafting rate of the guanidine salt polymer in the polystyrene-guanidine salt copolymer increases with the increase of epoxy group content in the polystyrene. As can be seen from the data in Examples 28 and 29 of Table 4, when the epoxy group content or the relative molecular mass of the polystyrene is too high, a large number of cross-linked structures will be generated during the internal mixing process.

[0141] Table 4. Grafting rate data of guanidine salt polymers in polystyrene-guanidine salt copolymer functional materials prepared in Examples 21-29 and their dispersion in ethyl acetate.

[0142]

[0143] Example 30: Preparation of functional materials of polystyrene-guanidine salt copolymer

[0144] 25.5g of the epoxy polystyrene SG-6 prepared in Example 6 and 4.5g of PHMG-L were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 150°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, which was designated as PSGP-10.

[0145] Example 31: Preparation of functional polystyrene-guanidine salt copolymer

[0146] 25.5g of the epoxy polystyrene SG-6 prepared in Example 6 and 4.5g of PHMG-L were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 170°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, denoted as PSGP-11.

[0147] Example 32: Preparation of functional materials of polystyrene-guanidine salt copolymer

[0148] 25.5g of the epoxy polystyrene SG-6 prepared in Example 6 and 4.5g of PHMG-L were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 180°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, which was designated as PSGP-12.

[0149] Example 33: Preparation of polystyrene-guanidine salt copolymer functional materials

[0150] 25.5g of the epoxy polystyrene SG-6 prepared in Example 6 and 4.5g of PHMG-L were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 190°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, which was designated as PSGP-13.

[0151] Example 34: Preparation of polystyrene-guanidine salt copolymer functional materials

[0152] 25.5g of the epoxy polystyrene SG-6 prepared in Example 6 and 4.5g of PHMG-L were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 200°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, which was designated as PSGP-14.

[0153] Example 35: Preparation of functional materials of polystyrene-guanidine salt copolymer

[0154] 25.5g of the epoxy polystyrene SG-6 prepared in Example 6 and 4.5g of PHMG-L were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 210°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, which was designated as PSGP-15.

[0155] Example 36: Preparation of functional materials of polystyrene-guanidine salt copolymer

[0156] 25.5g of the epoxy polystyrene SG-6 prepared in Example 6 and 4.5g of PPMG-L were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 170°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, which was designated as PSGP-16.

[0157] Table 5. Grafting rate data of guanidine salt polymers in polystyrene-guanidine salt copolymer functional materials prepared in Examples 30-36 and their dispersion in ethyl acetate.

[0158]

[0159] As can be seen from the data in Examples 30-35 in Table 5, as the mixing temperature increases, the grafting rate of guanidine salt polymer in polystyrene-guanidine salt copolymer functional materials continuously decreases: when the mixing temperature reaches 210°C, a large number of cross-linked structures exist in the mixing product.

[0160] Example 37: Preparation of functional materials of polystyrene-guanidine salt copolymer

[0161] 27g of the epoxy polystyrene SG-9 prepared in Example 9 and 3g of PHMG-O were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 170°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, which was designated as PSGP-17.

[0162] Example 38: Preparation of functional materials of polystyrene-guanidine salt copolymer

[0163] 25.5g of the epoxy polystyrene SG-9 prepared in Example 9 and 4.5g of PHMG-O were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 170°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, which was designated as PSGP-18.

[0164] Example 39: Preparation of polystyrene-guanidine salt copolymer functional materials

[0165] 24.9g of the epoxy polystyrene SG-9 prepared in Example 9 and 5.1g of PHMG-O were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 170°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, which was designated as PSGP-19.

[0166] Example 40: Preparation of functional polystyrene-guanidine salt copolymer

[0167] 24.6g of the epoxy polystyrene SG-9 prepared in Example 9 and 5.4g of PHMG-O were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 170°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, denoted as PSGP-20.

[0168] Example 41: Preparation of functional polystyrene-guanidine salt copolymer

[0169] 24g of the epoxy polystyrene SG-9 prepared in Example 9 and 6g of PHMG-O were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 170°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, denoted as PSGP-21.

[0170] Example 42: Preparation of polystyrene-guanidine salt copolymer functional materials

[0171] 22.5g of the epoxy polystyrene SG-9 prepared in Example 9 and 7.5g of PHMG-O were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 170°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, denoted as PSGP-22.

[0172] Example 43: Preparation of polystyrene-guanidine salt copolymer functional materials

[0173] 21g of the epoxy polystyrene SG-9 prepared in Example 9 and 9g of PHMG-O were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. Then, the powder was added to a mixer and mixed at 170°C and 60rpm for 8min. After cooling, the polystyrene-guanidine salt copolymer functional material was obtained, denoted as PSGP-23.

[0174] As can be seen from the data in Examples 37-43 in Table 6, the grafting rate of guanidine salt polymer in polystyrene-guanidine salt copolymer functional materials continuously decreases with the increase of guanidine salt polymer content.

[0175] Table 6. Grafting rate data of guanidine salt polymers in polystyrene-guanidine salt copolymer functional materials prepared in Examples 37-43 and their dispersion in ethyl acetate.

[0176]

[0177] Example 44: Preparation of polystyrene-guanidine salt copolymer functional materials

[0178] 664g of the epoxy polystyrene SG-9 prepared under the conditions of Example 9 and 136g of PHMG-O were placed in a high-speed pulverizer and pulverized for 30s to obtain a uniformly mixed powder. The powder was added to the feed hopper of a twin-screw extruder, and the mixture was extruded under the following conditions: a feed speed of 2 rpm, screw zone 1, 2, 3, 4, 5 temperatures of 120℃, 170℃, 170℃, 170℃, 170℃, and 160℃, and screw speed of 100 rpm. After cooling, a polystyrene-guanidine salt copolymer functional material, designated PSGP-24, was obtained. PSGP-24 can be completely dispersed in ethyl acetate, and its guanidine salt polymer grafting rate is 95.35%.

[0179] Example 45: Preparation of polystyrene-guanidine salt copolymer functional materials

[0180] 664g of the epoxy polystyrene SG-11 prepared in Example 11 and 136g of PHMG were pulverized in a high-speed pulverizer for 30s to obtain a uniformly mixed powder. The powder was added to the feed hopper of a twin-screw extruder. Under the conditions of a feed speed of 2 rpm, screw zone 1, 2, 3, 4, 5 and die head temperatures of 120℃, 170℃, 170℃, 170℃, 170℃ and 160℃ respectively, and screw speed of 100 rpm, the mixture was extruded and blended. After cooling, a polystyrene-guanidine salt copolymer functional material, denoted as PSGP-25, was obtained. PSGP-25 can be completely dispersed in ethyl acetate, and its guanidine salt polymer grafting rate is 96.64%.

[0181] Example 46: Preparation of Nylon-Guanidinium Salt Copolymer Masterbatch

[0182] The polystyrene-guanidine salt copolymer functional material PSGP-24 prepared in Example 44 was vacuum dried at 80°C for 24 hours and mixed with nylon 6 chips that were vacuum dried at 120°C for 48 hours at a mass ratio of 1:4. The mixture was then added to the feed hopper of a twin-screw extruder. The mixture was extruded under the following conditions: feed speed of 3 rpm, screw zone 1, 2, 3, 4, 5 and die head temperatures of 190°C, 245°C, 245°C, 245°C, 245°C and 235°C respectively, and screw speed of 100 rpm. After cooling, the mixture was pelletized and dried to obtain nylon-guanidine salt copolymer masterbatch 1 with a guanidine salt polymer content of 3.4 wt%.

[0183] Example 47: Preparation of Nylon-Guanidinium Salt Copolymer Masterbatch

[0184] The polystyrene-guanidine salt copolymer functional material PSGP-25 prepared in Example 45 was vacuum dried at 80°C for 24 hours and mixed with nylon 6 chips that were vacuum dried at 120°C for 48 hours at a mass ratio of 1:4. The mixture was then added to the feed hopper of a twin-screw extruder. The mixture was extruded under the following conditions: feed speed of 3 rpm, screw zone 1, 2, 3, 4, 5 and die head temperatures of 190°C, 245°C, 245°C, 245°C, 245°C and 235°C respectively, and screw speed of 100 rpm. After cooling, the mixture was pelletized and dried to obtain nylon-guanidine salt copolymer masterbatch 2 with a guanidine salt polymer content of 3.4 wt%.

[0185] Example 48: Preparation of Nylon-Guanidinium Salt Copolymer Masterbatch

[0186] The polystyrene-guanidine salt copolymer functional material PSGP-24 prepared in Example 44 was vacuum dried at 80°C for 24 hours and mixed with nylon 66 chips that were vacuum dried at 120°C for 48 hours at a mass ratio of 1:4. The mixture was then added to the feed hopper of a twin-screw extruder. The mixture was extruded under the following conditions: feed speed of 3 rpm, screw zone 1, 2, 3, 4, 5 and die head temperatures of 240°C, 270°C, 270°C, 270°C and 255°C respectively, and screw speed of 100 rpm. After cooling, the mixture was pelletized and dried to obtain nylon-guanidine salt copolymer masterbatch 3 with a guanidine salt polymer content of 3.4 wt%.

[0187] Example 49: Preparation of Nylon-Guanidinium Salt Copolymer Masterbatch

[0188] The polystyrene-guanidine salt copolymer functional material PSGP-24 prepared in Example 44 was vacuum dried at 80°C for 24 hours and nylon 56 chips were vacuum dried at 120°C for 48 hours. The mixture was then added to the feed hopper of a twin-screw extruder at a mass ratio of 1:3. The mixture was extruded under the following conditions: feed speed of 3 rpm, screw zone 1, 2, 3, 4, 5 and die head temperatures of 240°C, 270°C, 270°C, 270°C, 270°C and 260°C respectively, and screw speed of 100 rpm. After cooling, the mixture was pelletized and dried to obtain nylon-guanidine salt copolymer masterbatch 4 with a guanidine salt polymer content of 4.25 wt%.

[0189] Comparative Example 1: Preparation of Antibacterial Nylon 6 Masterbatch

[0190] 48g of PHMG and 752g of nylon 6 chips that were vacuum dried at 120℃ for 48h were pulverized and mixed in a high-speed pulverizer for 30s. The mixture was then added to the feed hopper of a twin-screw extruder. The extrusion was carried out under the following conditions: feed speed of 3rpm, screw zone 1, 2, 3, 4, 5 and die head temperatures of 215℃, 245℃, 245℃, 245℃ and 235℃ respectively, and screw speed of 100rpm. After cooling, the mixture was pelletized and dried to obtain antibacterial nylon 6 masterbatch 1 with a guanidine salt polymer content of 6wt%.

[0191] Comparative Example 2: Preparation of Antibacterial Nylon 6 Masterbatch

[0192] 48g of PHMG-O and 752g of nylon 6 chips that were vacuum dried at 120℃ for 48h were pulverized and mixed in a high-speed pulverizer for 30s. Then, the mixture was added to the feed hopper of a twin-screw extruder. The extrusion was carried out under the following conditions: feed speed of 3rpm, screw zone 1, 2, 3, 4, 5 and die head temperatures of 215℃, 245℃, 245℃, 245℃ and 235℃ respectively, and screw speed of 100rpm. After cooling, the mixture was pelletized and dried to obtain antibacterial nylon 6 masterbatch 2 with a guanidine salt polymer content of 6wt%.

[0193] Comparative Example 3: Preparation of Antibacterial Nylon 6 Masterbatch

[0194] 27.2g of PHMG-O, 80g of the epoxy polystyrene SG-9 prepared in Example 9, and 692.8g of nylon 6 chips dried under vacuum at 120℃ for 48h were pulverized and mixed in a high-speed pulverizer for 30s. The mixture was then added to the feed hopper of a twin-screw extruder. The mixture was extruded under the following conditions: feed speed of 3rpm, screw zone 1, 2, 3, 4, 5 and die head temperatures of 190℃, 240℃, 240℃, 240℃, 240℃ and 235℃ respectively, and screw speed of 100rpm. After cooling, the mixture was pelletized and dried to obtain antibacterial nylon 6 masterbatch 3 with a guanidine salt polymer content of 3.4wt%.

[0195] Comparative Example 4: Preparation of Nylon 6 Fibers

[0196] Nylon 6 chips were vacuum dried at 120℃ for 48 hours and then fed into the feed hopper of a spinning machine. Melt spinning was performed using a spinneret with 36 holes and a diameter of 0.3 mm. Pre-oriented yarns were obtained under the following conditions: screw zone 1-4 temperature, flange temperature, bend temperature, and housing temperature were 255-265℃, and the winding speed was 800 m / min. Using a parallel drawing machine, the pre-oriented yarns were hot-drawn to their maximum stretch ratio at a hot plate temperature of 120℃ and a hot plate temperature of 60℃ to obtain nylon 6 fibers, denoted as Nylon 6-f0.

[0197] Comparative Example 5: Preparation of Antibacterial Nylon 6 Fiber

[0198] The antibacterial nylon 6 masterbatch 1 and nylon 6 chips prepared in Comparative Example 1 were vacuum dried at 120℃ for 48 hours, and then mixed in a certain proportion to prepare blended chips with guanidine salt polymer contents of 1.5% and 2.0%. These were then added sequentially to the feed hopper of a spinning machine, and melt spinning was performed using a spinneret with 36 holes and a hole diameter of 0.3 mm. Pre-oriented yarns were obtained under the conditions of screw zone 1-4 temperature, flange temperature, bend temperature, and box temperature of 252-262℃, and winding speed of 800 m / min. Using a parallel drawing machine, the pre-oriented yarns were hot-drawn to the maximum stretch ratio under the conditions of hot plate temperature of 60℃ and hot plate temperature of 120℃ to obtain a series of nylon 6 fibers, denoted as antibacterial nylon 6-f1 and antibacterial nylon 6-f2, respectively.

[0199] Comparative Example 6: Preparation of Antibacterial Nylon 6 Fiber

[0200] The antibacterial nylon 6 masterbatch 2 and nylon 6 chips prepared in Comparative Example 2 were vacuum dried at 120℃ for 48 hours, and then mixed in a certain proportion to prepare a blended chip with a guanidine salt polymer content of 1.0%. This blend was added to the feed hopper of a spinning machine, and melt spinning was performed using a 36-hole spinneret with a 0.3mm orifice. Pre-oriented yarn was obtained under the following conditions: screw zone 1-4 temperature, flange temperature, bend temperature, and housing temperature were 255-262℃, and the winding speed was 800m / min. Using a parallel drawing machine, the pre-oriented yarn was hot-drawn to its maximum stretch ratio at a hot plate temperature of 120℃ and a hot plate temperature of 60℃ to obtain nylon 6 fiber, denoted as antibacterial nylon 6-f3.

[0201] Comparative Example 7: Preparation of Antibacterial Nylon 6 Fiber

[0202] The antibacterial nylon 6 masterbatch 3 and nylon 6 chips prepared in Comparative Example 3 were vacuum dried at 120℃ for 48 hours, and then mixed in a certain proportion to prepare a blend of chips with a guanidine salt polymer content of 1.0%. This blend was added to the feed hopper of a spinning machine, and melt spinning was performed using a spinneret with 36 holes and a pore size of 0.3 mm. Pre-oriented yarn was obtained under the conditions of screw zone 1-4 temperature, flange temperature, bend temperature, and box temperature of 255-262℃, and a winding speed of 800 m / min. Using a parallel drawing machine, the pre-oriented yarn was hot-drawn to its maximum stretch ratio under the conditions of a hot plate temperature of 60℃ and a hot plate temperature of 120℃ to obtain nylon 6 fiber, denoted as antibacterial nylon 6-f4.

[0203] Example 50: Preparation of antibacterial nylon 6 fiber

[0204] The nylon-guanidine salt copolymer masterbatch 1 and nylon 6 chips prepared in Example 46 were vacuum dried at 120°C for 48 hours, respectively. Then, they were mixed in a certain proportion to prepare a series of blended chips with guanidine salt polymer contents of 0.21%, 0.27%, 0.33%, 0.39%, and 0.57%. These blended chips were then added sequentially to the feed hopper of a spinning machine, and melt spinning was performed using a spinneret with 36 holes and a hole diameter of 0.3 mm. Pre-oriented yarns were obtained under the conditions of screw zone 1-4 temperature, flange temperature, bend temperature, and box temperature of 250-260°C, and winding speed of 800 m / min. Using a parallel drawing machine, under the conditions of a hot plate temperature of 60℃ and a hot plate temperature of 120℃, the pre-oriented yarn is hot-drawn to the maximum stretch ratio to obtain a series of nylon 6 fibers, which are respectively designated as antibacterial nylon 6-f5, antibacterial nylon 6-f6, antibacterial nylon 6-f7, antibacterial nylon 6-f8 and antibacterial nylon 6-f9.

[0205] Example 51: Preparation of antibacterial nylon 6 fiber

[0206] The nylon-guanidine salt copolymer masterbatch 2 and nylon 6 chips prepared in Example 47 were vacuum dried at 120°C for 48 hours, respectively. Then, they were mixed in a certain proportion to prepare blended chips with guanidine salt polymer contents of 0.21%, 0.27%, 0.33%, and 0.39%. These blended chips were then added sequentially to the feed hopper of a spinning machine, and melt spinning was performed using a 36-hole spinneret with an orifice diameter of 0.3 mm. Pre-oriented yarns were obtained under the following conditions: screw zone 1-4 temperature, flange temperature, bend temperature, and box temperature of 250-260°C, and winding speed of 800 m / min. Using a parallel drawing machine, under the conditions of a hot plate temperature of 60℃ and a hot plate temperature of 120℃, the pre-oriented yarn is hot-drawn to the maximum stretch ratio to obtain a series of nylon 6 fibers, which are respectively named antibacterial nylon 6-f10, antibacterial nylon 6-f11, antibacterial nylon 6-f12 and antibacterial nylon 6-f13.

[0207] Example 52: Preparation of antibacterial nylon 66 fiber

[0208] The nylon-guanidine salt copolymer masterbatch 3 and nylon 66 chips prepared in Example 48 were vacuum dried at 120°C for 48 hours, and then mixed in a certain proportion to prepare a series of blended chips. Pure nylon 66 chips and blended chips with guanidine salt polymer contents of 0.33% and 0.39% were sequentially added to the feed hopper of a spinning machine, and melt spinning was performed using a spinneret with 36 holes and a hole diameter of 0.3 mm. Pre-oriented yarn was obtained under the conditions of screw zone 1-4 temperature, flange temperature, bend temperature and box temperature of 290-305°C, and winding speed of 800 m / min. Using a parallel drawing machine, the pre-oriented yarn was hot-drawn to the maximum stretch ratio under the conditions of hot plate temperature of 60°C and hot plate temperature of 120°C to obtain a series of nylon 66 fibers, which were designated as nylon 66-f0, antibacterial nylon 66-f1 and antibacterial nylon 66-f2, respectively.

[0209] Example 53: Preparation of antibacterial nylon 56 fiber

[0210] The nylon-guanidine salt copolymer masterbatch 4 and nylon 56 chips prepared in Example 49 were vacuum dried at 120°C for 48 hours, and then mixed in a certain proportion to prepare a series of blended chips. Pure nylon 56 chips and blended chips with guanidine salt polymer contents of 0.33% and 0.39% were sequentially added to the feed hopper of a spinning machine, and melt spinning was performed using a spinneret with 36 holes and a hole diameter of 0.3 mm. Pre-oriented yarns were obtained under the conditions of screw zone 1-4 temperature, flange temperature, bend tube temperature and box temperature of 270-285°C, and winding speed of 800 m / min. Using a parallel drawing machine, the pre-oriented yarns were hot-drawn to the maximum stretch ratio under the conditions of hot plate temperature of 60°C and hot plate temperature of 120°C to obtain a series of nylon 56 fibers, which were designated as nylon 56-f0, antibacterial nylon 56-f1 and antibacterial nylon 56-f2, respectively.

[0211] Table 7 Mechanical and antibacterial properties of antibacterial polyamide fibers

[0212]

[0213] From the data in Table 7 of the antibacterial nylon 6-f1 and antibacterial nylon 6-f2 spun in Comparative Example 5, it can be seen that when antibacterial nylon 6 masterbatch 1 prepared in Comparative Example 1 (i.e., melt blending PHMG with nylon 6) is used to spin antibacterial nylon 6 fibers, the fibers only exhibit excellent antibacterial properties when the guanidine salt polymer content reaches 2.0 wt%. Compared with pure nylon 6 fibers (nylon 6-f0), its maximum stretch ratio and mechanical properties are significantly reduced.

[0214] From the data of antibacterial nylon 6-f3 spun in Comparative Example 6 in Table 7, it can be seen that when antibacterial nylon 6 masterbatch 2 prepared by Comparative Example 2 (i.e., melt blending PHMG-O with nylon 6) is used to spin antibacterial fibers, the fibers exhibit good antibacterial properties when the guanidine salt polymer content reaches 1.0 wt%. Compared with antibacterial nylon 6 masterbatch 1 prepared by direct blending PHMG with nylon 6, the amount of guanidine salt polymer required to spin antibacterial nylon 6 fibers is reduced. Correspondingly, the maximum stretch ratio and mechanical properties of the antibacterial fibers are significantly increased, but there is still a significant decrease compared with blank nylon 6 fibers.

[0215] From the data of antibacterial nylon 6-f4 spun in Comparative Example 7 in Table 7, it can be seen that when antibacterial nylon 6 masterbatch 3 prepared by Comparative Example 3 (i.e., one-step melt blending of 3.4 wt% PHMG-O, 10 wt% polyepoxy styrene copolymer and 86.6 wt% nylon 6) is used to spin antibacterial fibers, similar to antibacterial nylon 6 masterbatch 2 prepared by direct blending of PHMG-O and nylon 6, the fibers only exhibit good antibacterial properties when the content of guanidine salt polymer reaches 1.0 wt%. The mechanical properties of the fibers are slightly improved, but still have a large gap with the mechanical properties of blank nylon 6 fibers.

[0216] From the data in Table 7 for the antibacterial nylon 6 fibers (antibacterial nylon 6-f5-antibacterial nylon 6-f13) spun in Examples 50 and 51, the antibacterial nylon 66 fibers (antibacterial nylon 66-f1 and antibacterial nylon 66-f2) spun in Example 52, and the antibacterial nylon 56 fibers (antibacterial nylon 56-f1 and antibacterial nylon 56-f2) spun in Example 53, it can be seen that when using the nylon-guanidine salt copolymer masterbatch of the present invention to spin antibacterial nylon 6 fibers, antibacterial nylon 66 fibers, and antibacterial nylon 56 fibers, the fibers exhibit excellent antibacterial properties when the guanidine salt polymer content reaches 0.27 wt%, and the breaking strength of the obtained antibacterial fibers is only slightly lower than that of pure nylon fibers.

[0217] Therefore, it can be seen that the antibacterial masterbatch prepared by direct melt blending of guanidine salt polymer and nylon, and the antibacterial masterbatch prepared by one-step melt blending of guanidine salt polymer, epoxy polystyrene and nylon, compared with the nylon-guanidine salt copolymer masterbatch prepared by the two-step melt blending of the present invention (firstly, the guanidine salt polymer and epoxy polystyrene are melt blended to prepare polystyrene-guanidine salt copolymer functional material, and then the functional material is melt blended with nylon), require only a small amount of guanidine salt polymer to exhibit excellent antibacterial properties when preparing antibacterial nylon fibers, and the resulting antibacterial fibers also have excellent mechanical properties.

[0218] Figure 1The scanning electron microscope (SEM) image of the cross-section of the antibacterial nylon 6-f9 nascent fiber spun using the nylon-guanidine salt copolymer masterbatch of the present invention, after being brittlely broken in liquid nitrogen, and the Cl element distribution curve obtained by linear scanning of Cl element along the radial direction from the fiber center, show that the Cl element content gradually increases from the fiber center to the fiber surface, especially on the fiber surface, where the Cl element content increases significantly. This indicates that when the nylon-guanidine salt copolymer masterbatch prepared by the present invention is applied to the spinning of antibacterial fibers in the nylon system, the guanidine salt polymer is enriched on the surface of the antibacterial fiber, thereby enabling it to exert excellent antibacterial properties at a very low addition amount.

[0219] Table 8. Antibacterial properties of antibacterial polyamide fibers after 10 and 50 washes.

[0220]

[0221] As can be seen from Table 8, the antibacterial polyamide fiber prepared by the nylon-guanidine salt copolymer masterbatch prepared by the two-step melt blending of the present invention has excellent water wash resistance and still has excellent antibacterial properties after 50 water washes.

[0222] Although this disclosure has been described above through specific embodiments, it should be understood that those skilled in the art can devise various modifications, improvements, or equivalents to this disclosure within the spirit and scope of the appended solutions. Such modifications, improvements, or equivalents should also be considered to be included within the scope of protection claimed in this disclosure.

Claims

1. A method for preparing antibacterial polyamide fibers, characterized in that, The preparation method includes the following steps: (1) Styrene, functional monomers, initiators and chain transfer agents are added to a solvent, stirred and mixed evenly, and then heated to 50-85℃ for 9-12 hours. After cooling, the product is dropped into ethanol or methanol to precipitate. After filtration and drying, polyepoxy polystyrene is obtained. Or (2) Styrene, functional monomer and initiator are stirred and mixed evenly, then added to an aqueous solution containing dispersant, stirring is started, the temperature is raised to 60-90℃ and reacted for 7-11 hours, and after cooling, cleaning and drying, polyepoxy polystyrene is obtained; Or (3) Styrene, functional monomer and benzoyl peroxide initiator are stirred and mixed evenly, and then fed into the feed port of the twin-screw extruder. Under the condition that the temperature of the screw extruder is 80℃~160℃ in zones 1-16, the reaction is carried out for 6~30 minutes. After extrusion and cooling, polyepoxy polystyrene is obtained. (4) After the polyepoxy polystyrene prepared in step (1), step (2) or step (3) is mixed with the guanidine salt polymer at a mass ratio of 7:3 to 9:1, it is added to a two-roll mill, a Hack internal mixer, a single screw extruder or a twin screw extruder and mixed at 140 to 200°C for 6 to 20 minutes. After cooling, the polystyrene-guanidine salt copolymer functional material is obtained. (5) After mixing the polystyrene-guanidine salt copolymer functional material prepared in step (4) with nylon at a mass ratio of 3:17 to 3:7, add it to an open mill, Hack internal mixer, single screw extruder or twin screw extruder, and blend it at 5 to 30°C above the melting point of nylon for 6 to 30 minutes. After cooling, the nylon-guanidine salt copolymer masterbatch is obtained. (6) After the nylon-guanidine salt copolymer masterbatch prepared in step (5) and nylon are thoroughly dried, they are mixed evenly at a mass ratio of 1:24 to 1:4 and then melt-spun to obtain antibacterial polyamide fiber. The functional monomer is glycidyl methacrylate or glycidyl acrylate or a mixture thereof; in steps (1) and (3), the molar percentage of the functional monomer is based on the total amount of styrene and the functional monomer, and is 3.5% to 10.0%; in step (2), the molar percentage of the functional monomer is based on the total amount of styrene and the functional monomer, and is 5.0% to 11.0%. The epoxy polystyrene has a molar percentage of epoxy groups of 3.5% to 10% and a number average molecular weight of 3,000 to 20,000. The guanidine salt polymer has The structure shown, where Z - For Cl - ,Br - HSO4 - HCO3 - H2PO4 - CH3COO - Or CH3(CH2)16COO - m is a natural number from 2 to 20; R1 is The structure shown; R is H or The structure shown or a combination of the two; The nylon is selected from one of nylon 6, nylon 66, and nylon 56.

2. The method for preparing antibacterial polyamide fiber as described in claim 1, characterized in that, The polyepoxy polystyrene has a molar percentage of epoxy groups of 4.5% to 8.5%; the polyepoxy polystyrene has a number average molecular weight of 4000 to 15000; and the guanidine salt polymer has... The structure shown, where Z - For Cl - HCO3 - H2PO4 - Or CH3(CH2) 16 COO - m is a natural number from 2 to 20; R1 is The structure shown; R is The structure shown.

3. The method for preparing antibacterial polyamide fiber as described in claim 1, characterized in that, In step (1), the molar percentage of the functional monomer is based on the total amount of styrene and the functional monomer, and is 5.0% to 8.0%. The total concentration of styrene and functional monomers is based on the total mass of solvent, styrene and functional monomers, and ranges from 10 wt% to 40 wt%. The initiator is azobisisobutyronitrile or benzoyl peroxide; the molar percentage of the initiator is 1.0% to 3.0% based on the total amount of styrene and functional monomers. The chain transfer agent is one of dodecyl mercaptoethanol, mercaptoethanol, mercaptopropanol, and isopropanol; the molar percentage of the chain transfer agent is 0-1.2% based on the total amount of styrene and functional monomers. The solvent is one of toluene, xylene, tetrahydrofuran, and N,N'-dimethylformamide.

4. The method for preparing antibacterial polyamide fiber as described in claim 1, characterized in that, In step (2), the molar percentage of the functional monomer is based on the total amount of styrene and the functional monomer, and is 7.0% to 10.0%. The initiator is azobisisobutyronitrile or benzoyl peroxide; the molar percentage of the initiator is 1.3% to 3.8% based on the total amount of styrene and functional monomers. The ratio of the mass of water to the total mass of styrene and functional monomers is 7:1 to 10:1; The dispersant is one or a mixture of two of gelatin, polyvinyl alcohol, hydroxymethyl cellulose, hydroxyethyl cellulose, and sodium alginate; the mass percentage of the dispersant is 0.2 wt% to 0.5 wt% based on the mass of water.

5. The method for preparing antibacterial polyamide fiber as described in claim 1, characterized in that, In step (3), the molar percentage of the functional monomer is based on the total amount of styrene and the functional monomer, and is 6.0 to 9.0%. The molar percentage of the initiator is based on the total amount of styrene and functional monomers, and ranges from 1.0% to 5.0%.

6. The method for preparing an antibacterial polyamide fiber as described in claim 1, characterized in that, In step (4), the polyepoxy polystyrene and the guanidine salt polymer are mixed at a mass ratio of 4:1 to 17:3; the blending reaction temperature is 150 to 180°C; and the blending reaction time is 6 to 15 minutes.

7. The method for preparing antibacterial polyamide fiber as described in claim 1, characterized in that, In step (5), the polystyrene-guanidine salt copolymer functional material is mixed with the nylon at a mass ratio of 1:4 to 1:3; the blending reaction time is 6 to 15 minutes.

8. The method for preparing an antibacterial polyamide fiber as described in claim 1, characterized in that, In step (6), the nylon-guanidine salt copolymer masterbatch is mixed with the nylon at a mass ratio of 1:24 to 1:9; the melt spinning is carried out at a temperature of 250 to 305°C, a spinning speed of 800 to 1500 m / min, a spinneret orifice diameter of 0.2 to 0.5 mm, a stretching temperature of 60 to 120°C, and a stretching ratio of 3 to 4 times.

9. The antibacterial polyamide fiber prepared by the preparation method according to claim 1.

10. The application of the antibacterial polyamide fiber as described in claim 9 in the fields of clothing, bed sheets, socks, and carpets.

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