A rare earth modified antibacterial functional masterbatch for fiber and preparation method thereof

Abstract

The present invention provides a rare earth modified antibacterial functional masterbatch for fiber and a preparation method thereof. The masterbatch is made of the following raw materials in parts by weight: 5-20 parts of modified rare earth doped carbon quantum dot nanomaterials and 80-95 parts of polymer resin powder. The rare earth modified antibacterial functional masterbatch for fiber of the present invention has a simple preparation process, is used to prepare an antibacterial agent for fiber, is safe and non-toxic, and has good spinnability compared to other masterbatches. The prepared fiber has broad-spectrum antibacterial performance, high efficiency antibacterial, good stability, safety and environmental protection.

Description

Technical Field

[0001] The invention belongs to the field of textile weaving, and in particular relates to a rare earth modified antibacterial functional masterbatch for fiber and a preparation method thereof. Background Art

[0002] Antimicrobial agents for fibers can be mainly divided into organic antimicrobial agents, inorganic heavy metal antimicrobial agents and natural antimicrobial materials. Organic antimicrobial agents mainly include quaternary ammonium salts, guanidine compounds, ketones, pyridines, phenols, ethers, aldehydes, etc. Although they have good short-term rapid bactericidal effects, most of them have poor thermal stability, are easy to decompose, have poor durability, and are soluble and washable, which can cause certain damage to the environment and skin. Inorganic heavy metal antimicrobial agents mainly include nano-silver antimicrobial agents, copper antimicrobial agents, nano-zinc oxide antimicrobial agents, etc. They are resistant to high temperatures and washable, have broad-spectrum antimicrobial properties and long-lasting performance, but the heavy metal ions that are slowly released due to the antimicrobial effect can easily cause certain harm to the environment and human body. Natural antibacterial materials mainly include animal antibacterial agents (chitosan, chitin, insect antibacterial protein, etc.), plant antibacterial agents (artemisia, juniper, aloe, tea, pomegranate peel, Houttuynia cordata, etc.), and mineral antibacterial agents (aluminum, realgar, etc.). They are safe and pollution-free, but their antibacterial effects are average, their durability is poor, and they are difficult to process.

[0003] Rare earth has a special electron layer structure. The unpaired electrons in the 4f sublayer interact with the outer electrons of other elements, with high coordination activity and strong coordination ability. Rare earth ions interact with bacterial cell walls, cell membranes, DNA, enzymes, proteins, etc. in cells, change cell structure, hinder / interfere with the normal physiological activities of bacteria, inhibit bacterial growth and reproduction, and eventually cause bacterial death. Rare earth has good antibacterial properties, is non-toxic, safe and environmentally friendly, and its application in fiber antibacterial agents has a good application prospect. Summary of the invention

[0004] In view of this, the present invention aims to overcome the defects in the prior art and proposes a rare earth modified antibacterial functional masterbatch for fiber and a preparation method thereof.

[0005] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0006] A rare earth modified antibacterial functional masterbatch for fiber, the masterbatch is made of the following raw materials in parts by weight:

[0007] 5-20 parts of modified rare earth doped carbon quantum dot nanomaterials,

[0008] 80-95 parts of polymer resin powder;

[0009] The modified rare earth doped carbon quantum dot nanomaterial is prepared by a method comprising the following steps: rare earth doped carbon quantum dot nanomaterial Ln@CDs is mixed with a functional modifier and dried to obtain the modified rare earth doped carbon quantum dot nanomaterial.

[0010] Furthermore, the mass ratio of the rare earth doped carbon quantum dot nanomaterial Ln@CDs to the functional modifier is 90-99:1-10.

[0011] Furthermore, the rare earth doped carbon quantum dot nanomaterial Ln@CDs is prepared by a method comprising the following steps:

[0012] Step 1 is to uniformly mix the hydrated rare earth nitrate compound, the rare earth chloride, the polyvinyl alcohol and the deionized water, and then stir under heating conditions, and continue stirring after adjusting the pH value of the solution to obtain an intermediate product;

[0013] Step 2 is to filter the intermediate product, dry and calcine the upper solid to obtain the rare earth doped carbon quantum dot nanomaterial Ln@CDs.

[0014] The rare earth doped carbon quantum dot nanomaterial Ln@CDs uses carbon quantum dot material as a carrier, and by loading different rare earth ions, the rare earth ions are mainly lanthanum / cerium ions, and are supplemented by samarium / gadolinium ions, so as to give full play to the advantages of carbon quantum dot material such as large specific surface area and good biocompatibility, and produce a synergistic antibacterial effect with the incorporated rare earth ions, and jointly enhance the antibacterial performance of the material (it has a strong bactericidal effect and good biocompatibility for both Gram-positive and Gram-negative bacteria); at the same time, using carbon quantum dot material as a carrier, more doping active sites are provided to the rare earth ions, the agglomeration of the material is reduced, and the material is given a nanoparticle size and a higher rare earth ion doping rate, which is more conducive to giving full play to the antibacterial performance of the material.

[0015] Furthermore, the mass ratio of the hydrated rare earth nitrate compound, rare earth chloride, polyvinyl alcohol and deionized water in step 1 is 20-60:3-15:1-10:150-350; the hydrated rare earth nitrate compound in step 1 is at least one of lanthanum nitrate hexahydrate or cerium nitrate hexahydrate; and the rare earth chloride is at least one of samarium chloride or gadolinium chloride.

[0016] Furthermore, the pH value of the solution in the step of adjusting the pH value of the solution in step 1 is 9-12; the temperature of the heating step in step 1 is 100-300° C., and the stirring time is 2-6 hours; and the time of the continued stirring step in step 1 is 2-6 hours.

[0017] Furthermore, the temperature of the drying step in step 2 is 70-110° C.; the temperature of the calcining step in step 2 is 500-1200° C., and the time is 2-4 hours; the particle size of the rare earth doped carbon quantum dot nanomaterial Ln@CDs is 50-300 nm.

[0018] Furthermore, the functional modifier comprises component A, component B and component C in a mass ratio of 10:3-10:3-10; the component A is at least one of γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane or γ-(2,3-epoxypropoxy)propyltrimethoxysilane; the component B is at least one of stearic acid and its metal salt lubricants, ester lubricants, paraffin and hydrocarbon lubricants; the component C is at least one of a phenolic antioxidant, a phosphite auxiliary antioxidant or a thioester auxiliary antioxidant.

[0019] The functional modifier described above modifies the functional groups on the surface of Ln@CDs, thereby obtaining good chemical activity, and easily forming strong interactions or chemical bonds with the polymer matrix resin, achieving good dispersion of Ln@CDs and good compatibility with the polymer matrix resin, reducing the problem of easy agglomeration of Ln@CDs nanomaterials due to their small particle size, so that their antibacterial properties can be effectively exerted, while not affecting the mechanical properties of the polymer material, thereby ensuring the excellent processability, good spinnability and long-term thermal stability of the subsequent masterbatch. Among them, component A is mainly used to improve the dispersibility of the powder in the matrix; component B is mainly used to increase the lubricity between materials and improve fluidity; component C is mainly used to provide excellent processability and long-term thermal stability for the masterbatch, while preventing the molecular weight change caused by oxidative degradation of the masterbatch during post-processing and spinning, and preventing discoloration; the thermal stability of the masterbatch is improved by synergistic anti-oxidation.

[0020] Furthermore, the polymer resin powder is obtained by grinding and drying the polymer resin; the temperature of the drying step is 90-130° C. and the time is 10-24 hours; the polymer resin is at least one of PA, PET, PBT, PLA, TPU or PE; and the particle size of the polymer resin powder is 200-1000 nm.

[0021] The preparation method of the rare earth modified antibacterial functional masterbatch for fiber comprises the following steps: uniformly mixing the modified rare earth doped carbon quantum dot nanomaterial and the polymer resin powder, then blending and melt extruding the mixture, cooling and solidifying the product, pelletizing and drying to obtain the rare earth modified antibacterial functional masterbatch for fiber.

[0022] Furthermore, the granulator speed in the blending melt extrusion step is 100-400 r / min, and the melting temperature is 120-280°C.

[0023] A method for preparing rare earth antibacterial functional fiber comprises the following steps:

[0024] The fiber rare earth modified antibacterial functional masterbatch is mixed with a polymer high molecular resin and then melt-spun at 150-300° C. to obtain the rare earth antibacterial functional fiber.

[0025] The mass ratio of the rare earth modified antibacterial functional masterbatch for fiber to the polymer high molecular resin is 1-30:70-99; the polymer high molecular resin is at least one of PA, PET, PBT, PLA, TPU or PE.

[0026] Compared with the prior art, the present invention has the following advantages:

[0027] The rare earth modified antibacterial functional masterbatch for fiber of the present invention has a simple preparation process, is safe and non-toxic for preparing the antibacterial agent for fiber, and has good spinnability compared with other masterbatches. The prepared fiber has broad-spectrum antibacterial performance, high efficiency antibacterial, good stability, safety and environmental protection. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is a curve of component pressure change during the spinning process of the rare earth modified antibacterial functional masterbatch described in Example 1 of the present invention. DETAILED DESCRIPTION

[0029] Unless otherwise defined, the technical terms used in the following examples have the same meanings as those generally understood by those skilled in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods, unless otherwise specified, are all conventional methods.

[0030] The present invention will be described in detail below with reference to the embodiments.

[0031] Example 1

[0032] A method for preparing rare earth antibacterial functional fiber comprises the following steps:

[0033] (1) Preparation of rare earth doped carbon quantum dot nanomaterials:

[0034] Weigh 30 parts of lanthanum nitrate hexahydrate, 10 parts of samarium chloride, 6 parts of polyvinyl alcohol and 200 parts of deionized water by mass, stir and mix them well, transfer the obtained mixture into a hydrothermal reactor, stir at 230° C. for 4 hours, add saturated sodium bicarbonate solution to adjust the pH value to 11, and continue stirring for 3 hours to obtain an intermediate product, filter the intermediate product, take the upper solid after filtration and dry it in an oven at 80° C., add the dried sample into a muffle furnace and calcine at 1000° C. for 3 hours to prepare a rare earth doped carbon quantum dot nanomaterial with a particle size of 190 nm;

[0035] (2) Functional modification of rare earth doped carbon quantum dots nanomaterials:

[0036] Weigh 10 parts by mass of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, 2 parts by mass of zinc stearate, 3 parts by mass of ethylene-vinyl acetate copolymer wax, 3 parts by mass of 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and 1 part by mass of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, mix them thoroughly and evenly to obtain a functional modifier, weigh the above 3 parts by mass of the functional modifier and 97 parts by mass of the rare earth doped carbon quantum dot nanomaterial, put them into a high-speed mixer, mix them at a high speed for 10 minutes, and then dry them in air to obtain a modified rare earth doped carbon quantum dot nanomaterial;

[0037] (3) Preparation of polymer resin powder:

[0038] The PET resin was ground and then dried in a vacuum oven at 130°C for 12 hours to obtain PET resin powder;

[0039] (4) Preparation of rare earth modified antibacterial functional masterbatch for fiber:

[0040] Weigh the above 10 parts of modified rare earth doped carbon quantum dot nanomaterials and 90 parts of PET powder by weight percentage, divide them into 3 batches, alternately put them into a high-speed mixer for high and low speed mixing, mix them thoroughly, put the mixed materials into a twin-screw granulator for blending and melt extrusion, the twin-screw granulator speed is 350r / min, the melting temperature is 265°C, and after cooling and solidification, pelletize and dry to obtain rare earth modified antibacterial functional masterbatch for fiber;

[0041] (5) Preparation of rare earth antibacterial functional fibers:

[0042] 10 parts of rare earth modified antibacterial functional masterbatch and 90 parts of PET resin after drying are weighed according to weight percentage and added into a melt spinning machine. The spinning temperature is 290°C. The mixture is heated and melted and extruded by a screw. After being metered by a metering pump, it is transported to a spinning box, sprayed out through a spinneret, cooled by side blowing or ring blowing, oiled, wound into a yarn cake, and twisted and deformed by a texturing machine to obtain stretched and deformed rare earth antibacterial polyester.

[0043] Example 2

[0044] A method for preparing rare earth antibacterial functional fiber comprises the following steps:

[0045] (1) Preparation of rare earth doped carbon quantum dot nanomaterials:

[0046] Weigh 40 parts of cerium nitrate hexahydrate, 5 parts of samarium chloride, 5 parts of gadolinium chloride, 8 parts of polyvinyl alcohol and 230 parts of deionized water by mass, stir and mix them evenly, transfer the obtained mixture into a hydrothermal reactor, stir at 250°C for 3 hours, add saturated sodium bicarbonate solution to adjust the pH value to 10, and continue stirring for 3 hours to obtain an intermediate product, filter the intermediate product, take the upper solid after filtration and dry it in an oven at 90°C, add the dried sample into a muffle furnace and calcine at 900°C for 3 hours to prepare a rare earth doped carbon quantum dot nanomaterial with a particle size of 210 nm;

[0047] (2) Functional modification of rare earth doped carbon quantum dots nanomaterials:

[0048] Weigh 10 parts of γ-aminopropyl triethoxysilane, 3 parts of pentaerythritol stearate, 2 parts of polyamide wax, 3 parts of N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide), and 1 part of bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphate by mass and mix them evenly to obtain a functional modifier, weigh 4 parts of the above functional modifiers and 96 parts of rare earth doped carbon quantum dot nanomaterials by mass, put them into a high-speed mixer, mix them at high speed for 10 minutes, and then dry them in air to obtain a modified rare earth doped carbon quantum dot nanomaterial;

[0049] (3) Preparation of polymer resin powder:

[0050] The PA resin was ground and then dried in a vacuum oven at 100°C for 18 hours to obtain PA resin powder;

[0051] (4) Preparation of rare earth modified antibacterial functional masterbatch for fiber:

[0052] Weigh the above 8 parts of modified rare earth doped carbon quantum dot nanomaterials and 92 parts of PA powder by weight percentage, divide them into 3 batches, alternately put them into a high-speed mixer for high and low speed mixing, mix them thoroughly, put the mixed materials into a twin-screw granulator for blending and melt extrusion, the speed of the twin-screw granulator is 220r / min, the melting temperature is 240°C, and after cooling and solidification, pelletize and dry to obtain rare earth modified antibacterial functional masterbatch for fiber;

[0053] (5) Preparation of rare earth antibacterial functional fibers:

[0054] 25 parts of rare earth modified antibacterial functional masterbatch and 75 parts of PA resin after drying are weighed according to weight percentage and added into a melt spinning machine. The spinning temperature is 260°C. The mixture is heated and melted by a screw, and is transported to a spinning box after being metered by a metering pump. It is ejected through a spinneret, cooled by side blowing or ring blowing, oiled, wound into a silk cake, and twisted and deformed by a texturing machine to obtain stretched and deformed rare earth antibacterial nylon.

[0055] Example 3

[0056] A method for preparing rare earth antibacterial functional fiber comprises the following steps:

[0057] (1) Preparation of rare earth doped carbon quantum dot nanomaterials:

[0058] Weigh 25 parts of lanthanum nitrate hexahydrate, 25 parts of cerium nitrate hexahydrate, 10 parts of gadolinium chloride, 9 parts of polyvinyl alcohol, and 280 parts of deionized water by mass, stir them thoroughly and mix them evenly, transfer the obtained mixture into a hydrothermal reactor, stir at 270°C for 4 hours, add saturated sodium bicarbonate solution to adjust the pH value to 10, and continue stirring for 4 hours to obtain an intermediate product, filter the intermediate product, take the upper solid after filtration and dry it in an oven at 100°C, add the dried sample into a muffle furnace and calcine at 1100°C for 3 hours to prepare a rare earth doped carbon quantum dot nanomaterial with a particle size of 260nm;

[0059] (2) Functional modification of rare earth doped carbon quantum dots nanomaterials:

[0060] Weigh 10 parts by mass of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 3 parts of polyethylene wax, 2 parts of ethylenebisstearamide, 3 parts of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and 1 part of bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphate, and mix them evenly to obtain a functional modifier; weigh 6 parts of the above functional modifiers and 94 parts of rare earth doped carbon quantum dot nanomaterials by mass, put them into a high-speed mixer, mix them at a high speed for 10 minutes, and then dry them in air to obtain a modified rare earth doped carbon quantum dot nanomaterial;

[0061] (3) Preparation of polymer resin powder:

[0062] The PE resin was ground and then dried in a vacuum oven at 90°C for 10 h to obtain PE resin powder;

[0063] (4) Preparation of rare earth modified antibacterial functional masterbatch for fiber:

[0064] Weigh the above 12 parts of modified rare earth doped carbon quantum dot nanomaterials and 88 parts of PE powder by weight percentage, divide them into 3 batches, alternately put them into a high-speed mixer for high and low speed mixing, mix them thoroughly, put the mixed materials into a twin-screw granulator for blending and melt extrusion, the twin-screw granulator speed is 300r / min, the melting temperature is 135°C, and after cooling and solidification, pelletize and dry to obtain rare earth modified antibacterial functional masterbatch for fiber;

[0065] (5) Preparation of rare earth antibacterial functional fibers:

[0066] 25 parts of rare earth modified antibacterial functional masterbatch and 75 parts of PE resin after drying are weighed according to weight percentage and added into a melt spinning machine. The spinning temperature is 160°C. The mixture is heated and melted by a screw, and is transported to a spinning box after being metered by a metering pump. It is ejected through a spinneret, cooled by side blowing or ring blowing, oiled, wound into a yarn cake, and twisted and deformed by a texturing machine to obtain stretched and deformed rare earth antibacterial ethylene.

[0067] Comparative Example 1

[0068] A method for preparing rare earth antibacterial functional fiber comprises the following steps:

[0069] (1) Preparation of rare earth doped carbon quantum dot nanomaterials:

[0070] Weigh 30 parts of lanthanum nitrate hexahydrate, 10 parts of samarium chloride, 6 parts of polyvinyl alcohol and 200 parts of deionized water by mass, stir and mix them well, transfer the obtained mixture into a hydrothermal reactor, stir at 230° C. for 4 hours, add saturated sodium bicarbonate solution to adjust the pH value to 11, and continue stirring for 3 hours to obtain an intermediate product, filter the intermediate product, take the upper solid after filtration and dry it in an oven at 80° C., add the dried sample into a muffle furnace and calcine at 1000° C. for 3 hours to prepare a rare earth doped carbon quantum dot nanomaterial with a particle size of 190 nm;

[0071] (2) Functional modification of rare earth doped carbon quantum dots nanomaterials:

[0072] Weigh 3 parts of tris(2,4-di-tert-butylphenyl) phosphite and 97 parts of rare earth-doped carbon quantum dot nanomaterials by mass, put them into a high-speed mixer, mix them at high speed for 10 minutes, and then dry them in air to obtain modified rare earth-doped carbon quantum dot nanomaterials;

[0073] (3) Preparation of polymer resin powder:

[0074] The PET resin was ground and then dried in a vacuum oven at 130°C for 12 hours to obtain PET resin powder;

[0075] (4) Preparation of rare earth modified antibacterial functional masterbatch for fiber:

[0076] Weigh the above 10 parts of modified rare earth doped carbon quantum dot nanomaterials and 90 parts of PET powder by weight percentage, divide them into 3 batches, alternately put them into a high-speed mixer for high and low speed mixing, mix them thoroughly, put the mixed materials into a twin-screw granulator for blending and melt extrusion, the twin-screw granulator speed is 350r / min, the melting temperature is 265°C, and after cooling and solidification, pelletize and dry to obtain rare earth modified antibacterial functional masterbatch for fiber;

[0077] (5) Preparation of rare earth antibacterial functional fibers:

[0078] 10 parts of rare earth modified antibacterial functional masterbatch and 90 parts of PET resin after drying are weighed according to weight percentage and added into a melt spinning machine. The spinning temperature is 290°C. The mixture is heated and melted and extruded by a screw. After being metered by a metering pump, it is transported to a spinning box, sprayed out through a spinneret, cooled by side blowing or ring blowing, oiled, wound into a yarn cake, and twisted and deformed by a texturing machine to obtain stretched and deformed rare earth antibacterial polyester.

[0079] Comparative Example 2

[0080] A method for preparing rare earth antibacterial functional fiber comprises the following steps:

[0081] (1) Preparation of rare earth doped carbon quantum dot nanomaterials:

[0082] Weigh 30 parts of lanthanum nitrate hexahydrate, 10 parts of samarium chloride, 6 parts of polyvinyl alcohol and 200 parts of deionized water by mass, stir and mix them well, transfer the obtained mixture into a hydrothermal reactor, stir at 230° C. for 4 hours, add saturated sodium bicarbonate solution to adjust the pH value to 11, and continue stirring for 3 hours to obtain an intermediate product, filter the intermediate product, take the upper solid after filtration and dry it in an oven at 80° C., add the dried sample into a muffle furnace and calcine at 1000° C. for 3 hours to prepare a rare earth doped carbon quantum dot nanomaterial with a particle size of 190 nm;

[0083] (2) Preparation of polymer resin powder:

[0084] The PET resin was ground and then dried in a vacuum oven at 130°C for 12 hours to obtain PET resin powder;

[0085] (3) Preparation of rare earth antibacterial functional masterbatch for fiber:

[0086] Weigh the above 10 parts of rare earth doped carbon quantum dot nanomaterials and 90 parts of PET powder by weight percentage, divide them into 3 batches, alternately put them into a high-speed mixer for high and low speed mixing, mix them thoroughly, put the mixed materials into a twin-screw granulator for blending and melt extrusion, the speed of the twin-screw granulator is 350r / min, the melting temperature is 265°C, and after cooling and solidification, pelletize and dry to obtain rare earth antibacterial functional masterbatch for fiber;

[0087] (4) Preparation of rare earth antibacterial functional fibers:

[0088] 10 parts of rare earth antibacterial functional masterbatch and 90 parts of PET resin after drying are weighed according to weight percentage and added into a melt spinning machine. The spinning temperature is 290°C. The mixture is heated and melted by a screw, and is transported to a spinning box after being metered by a metering pump. It is ejected through a spinneret, cooled by side blowing or ring blowing, oiled, wound into a yarn cake, and twisted and deformed by a texturing machine to obtain stretched and deformed rare earth antibacterial polyester.

[0089] Comparative Example 3

[0090] A method for preparing rare earth antibacterial functional fiber comprises the following steps:

[0091] (1) Preparation of rare earth-doped nanomaterials:

[0092] Weigh 30 parts of lanthanum nitrate hexahydrate, 10 parts of samarium chloride and 150 parts of deionized water by mass, stir and mix them well, transfer the obtained mixture into a hydrothermal reactor, stir at 230°C for 4 hours, add saturated sodium bicarbonate solution to adjust the pH value to 11, and continue stirring for 3 hours to obtain an intermediate product, filter the intermediate product, take the upper solid after filtration and dry it in an oven at 80°C, add the dried sample into a muffle furnace and calcine at 1000°C for 3 hours to prepare a rare earth-doped nanomaterial with a particle size of 400nm;

[0093] (2) Functional modification of rare earth-doped nanomaterials:

[0094] Weigh 10 parts by mass of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, 2 parts by mass of zinc stearate, 3 parts by mass of ethylene-vinyl acetate copolymer wax, 3 parts by mass of 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and 1 part by mass of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, mix them thoroughly and evenly to obtain a functional modifier, weigh the above 3 parts by mass of the functional modifier and 97 parts by mass of the rare earth-doped nanomaterial, put them into a high-speed mixer, mix them at a high speed for 10 minutes, and then dry them in air to obtain a modified rare earth-doped nanomaterial;

[0095] (3) Preparation of polymer resin powder:

[0096] The PET resin was ground and then dried in a vacuum oven at 130°C for 12 hours to obtain PET resin powder;

[0097] (4) Preparation of rare earth modified antibacterial functional masterbatch for fiber:

[0098] Weigh the above 10 parts of modified rare earth doped nanomaterials and 90 parts of PET powder by weight percentage, divide them into 3 batches, alternately put them into a high-speed mixer for high and low speed mixing, mix them thoroughly, put the mixed materials into a twin-screw granulator for blending and melt extrusion, the speed of the twin-screw granulator is 350r / min, the melting temperature is 265°C, and after cooling and solidification, pelletize and dry to obtain rare earth modified antibacterial functional masterbatch for fiber;

[0099] (5) Preparation of rare earth antibacterial functional fibers:

[0100] 10 parts of rare earth modified antibacterial functional masterbatch and 90 parts of PET resin after drying are weighed according to weight percentage and added into a melt spinning machine. The spinning temperature is 290°C. The mixture is heated and melted and extruded by a screw. After being metered by a metering pump, it is transported to a spinning box, sprayed out through a spinneret, cooled by side blowing or ring blowing, oiled, wound into a yarn cake, and twisted and deformed by a texturing machine to obtain stretched and deformed rare earth antibacterial polyester.

[0101] Comparative Example 4

[0102] A method for preparing fiber comprises the following steps:

[0103] 100 parts of dried PET resin are weighed by weight percentage and added into a melt spinning machine, the spinning temperature is 290°C, the resin is heated and melted by a screw, and then transported to a spinning box after being metered by a metering pump, and then ejected from a spinneret, cooled by side blowing or ring blowing, oiled, wound into a silk cake, and twisted and deformed by a texturing machine to obtain stretched and deformed polyester fibers.

[0104] The antibacterial fibers prepared in the examples and comparative examples were subjected to the following tests:

[0105] Test example 1:

[0106] During the melt spinning process, the pressure change of the spinning assembly provides a favorable reference for continuous and stable production. If the assembly pressure is too low, it is easy to leak pulp and the spinneret will be deformed. If the assembly pressure rises too fast, the assembly replacement cycle will be shortened. Appropriate spinning pressure can enhance the filtering effect, reduce thermal degradation, reduce the breakage rate, and improve the quality. The assembly pressure of each embodiment and comparative example spinning process was tracked and monitored to obtain Figure 1 Component pressure variation curve shown.

[0107] Test 2:

[0108] The antibacterial fibers prepared in the examples and comparative examples were subjected to antibacterial tests according to GB / T 20944.3-2008 “Evaluation of antibacterial properties of textiles Part 3 Oscillation method”. The test results are shown in Table 1.

[0109] pass Figure 1 As can be seen from Table 1, the antibacterial rate of the polyester fiber in Comparative Example 4 without adding rare earth-doped carbon quantum dot nanomaterials against Escherichia coli, Staphylococcus aureus and Candida albicans is 0%. The polyester fiber itself does not have antibacterial properties. The pressure of the components rises slowly during the spinning process, and the fiber has good spinnability.

[0110] pass Figure 1 As can be seen from Table 1, in Examples 1-3, the mass percentages of modified rare earth-doped carbon quantum dot nanomaterials in the fibers are 1%, 2%, and 3%, respectively. As the content increases, the antibacterial rate of the fiber against Escherichia coli, Staphylococcus aureus, and Candida albicans gradually increases, and it has a strong bactericidal effect on both Gram-positive and Gram-negative bacteria. When the content is 3%, there are a few floating silks and broken ends. This may be because when the content of modified rare earth-doped carbon quantum dot nanomaterials is high, a small part of the agglomeration occurs, and it cannot be evenly distributed on the surface of the matrix, affecting the stability of spinning. It shows that when the rare earth-modified antibacterial functional masterbatch is added to prepare the fiber, when the content of modified rare earth-doped carbon quantum dot nanomaterials in the fiber is less than 3%, continuous and stable production can be achieved within a certain period of time, and it has good spinnability and antibacterial properties.

[0111] pass Figure 1As can be seen from Table 1, in Comparative Example 3, the rare earth-doped nanomaterials were prepared by ordinary methods, and no carbon quantum dots were produced. The antibacterial rate of the fiber against Escherichia coli, Staphylococcus aureus, and Candida albicans was greatly reduced, and there were more floating fibers and broken ends during the spinning process, the pressure of the assembly rose quickly, and the spinnability was poor. This shows that there is no carbon quantum dot material to provide a doping carrier to produce synergistic antibacterial with rare earth ions, the rare earth-doped nanomaterials have partially agglomerated, the antibacterial properties of the materials cannot be fully exerted, the antibacterial rate is significantly reduced, the spinneret is blocked during the spinning process, the pressure of the assembly rises quickly, and the breakage rate is high.

[0112] Comparative Examples 1 and 2, respectively, use conventional modifying agents and do not perform functional modification of rare earth doped carbon quantum dot nanomaterials. Compared with Example 1, the antibacterial rate is much lower, there are a few floating fibers and broken ends during the spinning process, the pressure of the assembly rises quickly, and the spinnability is poor. This shows that the rare earth doped carbon quantum dot nanomaterials are modified with conventional reagents or are not functionally modified, and are added as masterbatches to polymer resins for melt spinning. The compatibility between the functional components and the polymer matrix resin is poor, and the dispersibility and fluidity in the matrix are poor. The stability during the spinning process is poor, resulting in a decrease in antibacterial performance and poor spinnability.

[0113] Table 1 Antibacterial properties and spinnability of fibers

[0114]

[0115] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A rare earth modified antibacterial functional masterbatch for fiber, characterized in that: The masterbatch is made from the following raw materials in parts by weight: 5-20 parts of modified rare earth doped carbon quantum dot nanomaterials, 80-95 parts of polymer resin powder; The modified rare earth doped carbon quantum dot nanomaterial is prepared by a method comprising the following steps: mixing and drying the rare earth doped carbon quantum dot nanomaterial Ln@CDs with a functional modifier to obtain the modified rare earth doped carbon quantum dot nanomaterial; The mass ratio of the rare earth doped carbon quantum dot nanomaterial Ln@CDs to the functional modifier is 90-99:1-10; The functional modifier comprises component A, component B and component C in a mass ratio of 10:3-10:3-10; the component A is at least one of γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane or γ-(2,3-epoxypropoxy)propyltrimethoxysilane; the component B is at least one of stearic acid and its metal salt lubricants, ester lubricants, paraffin and hydrocarbon lubricants; the component C is at least one of phenolic antioxidants, phosphite auxiliary antioxidants or thioester auxiliary antioxidants; The rare earth doped carbon quantum dot nanomaterial Ln@CDs is prepared by a method comprising the following steps: Step 1 is to uniformly mix the hydrated rare earth nitrate compound, the rare earth chloride, the polyvinyl alcohol and the deionized water, and then stir under heating conditions, and continue stirring after adjusting the pH value of the solution to obtain an intermediate product; Step 2 is to filter the intermediate product, dry and calcine the obtained upper solid to obtain the rare earth doped carbon quantum dot nanomaterial Ln@CDs; The mass ratio of the hydrated rare earth nitrate compound, rare earth chloride, polyvinyl alcohol and deionized water in step 1 is 20-60:3-15:1-10:150-350; the hydrated rare earth nitrate compound in step 1 is at least one of lanthanum nitrate hexahydrate or cerium nitrate hexahydrate; and the rare earth chloride is at least one of samarium chloride or gadolinium chloride.

2. The rare earth modified antibacterial functional masterbatch for fiber according to claim 1, characterized in that: The pH value of the solution in the step of adjusting the pH value of the solution in step 1 is 9-12; the temperature of the heating step in step 1 is 100-300° C., and the stirring time is 2-6 hours; the time of the continued stirring step in step 1 is 2-6 hours.

3. The rare earth modified antibacterial functional masterbatch for fiber according to claim 1, characterized in that: The temperature of the drying step in step 2 is 70-110° C.; the temperature of the calcination step in step 2 is 500-1200° C., and the time is 2-4 hours; the particle size of the rare earth doped carbon quantum dot nanomaterial Ln@CDs is 50-300 nm.

4. The rare earth modified antibacterial functional masterbatch for fiber according to claim 1, characterized in that: The polymer resin powder is obtained by grinding and drying the polymer resin; the temperature of the drying step is 90-130° C. and the time is 10-24 hours; the polymer resin is at least one of PA, PET, PBT, PLA, TPU or PE; and the particle size of the polymer resin powder is 200-1000 nm.

5. The method for preparing the rare earth modified antibacterial functional masterbatch for fiber according to any one of claims 1 to 4, characterized in that: The method comprises the following steps: uniformly mixing the modified rare earth doped carbon quantum dot nanomaterial and polymer resin powder, then performing blending and melt extrusion, cooling and solidifying the product, and obtaining the rare earth modified antibacterial functional masterbatch for fiber after pelletizing and drying.

6. The method for preparing the rare earth modified antibacterial functional masterbatch for fiber according to claim 5, characterized in that: The granulator speed in the blending and melting extrusion step is 100-400r / min, and the melting temperature is 120-280°C.

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