High-performance real silk fiber / lyocell fiber blended fabric and preparation method thereof

Abstract

The invention discloses a high-performance real silk fiber / lyocell fiber blended fabric and a preparation method thereof, and relates to the technical field of blended fabrics. The high-performance real silk fiber / lyocell fiber blended fabric is prepared from the following raw materials in parts by weight: 25 to 35 parts of real silk fiber, 65 to 75 parts of lyocell fiber, 10 to 15 parts of antibacterial and antistatic composite functional additive, 10 to 20 parts of cross-linking agent, 15 to 20 parts of softening agent and 900 to 1100 parts of deionized water. The silk fiber / lyocell fiber blended fabric prepared by the invention has excellent mechanical property, washing resistance, antistatic property and antibacterial property.

Description

Technical Field

[0001] This invention relates to the field of blended fabric technology, specifically to a high-performance silk / lyocell blended fabric and its preparation method. Background Technology

[0002] Silk fiber, as a natural protein fiber, possesses excellent skin-friendliness, softness, luster, and breathability, holding an irreplaceable position in high-end clothing, intimate apparel, and home textiles. However, the molecular structure of silk fiber contains numerous polar groups such as amide bonds, hydroxyl groups, and amino groups, resulting in a flexible molecular chain and low crystallinity. Under washing conditions, it is prone to molecular chain rearrangement and structural relaxation, leading to poor fabric dimensional stability, high shrinkage, and easy deformation. Dry cleaning is typically the only option, severely limiting the widespread application of silk fabrics in everyday wear. Lyocell fiber, a regenerated cellulose fiber made from natural cellulose, possesses good mechanical strength, washability, moisture absorption and breathability, and environmentally friendly properties, making it widely used in clothing and home textiles. Blending silk and lyocell fibers can, to a certain extent, balance the high-end texture of silk with the mechanical stability of lyocell, representing an important development direction for high-end functional textile materials. However, existing silk / lyocell blended fabrics still have shortcomings such as insufficient antibacterial and antistatic properties. Therefore, developing a silk / lyocell blended fabric with excellent antibacterial, antistatic, mechanical, and washability properties is of great application significance.

[0003] Chinese invention patent CN112442779A discloses a tensile and tear-resistant blended fabric and its preparation method. First, a guanidine-modified mosquito repellent liquid is prepared. Then, an oligomeric silsesquioxane and a metal-organic framework are composited and modified with amino groups to obtain a carrier. This carrier is then mixed into a viscose fiber spinning solution to produce modified viscose fiber. The modified viscose fiber in this invention contains a large number of cationic groups such as guanidine and amino groups, while the modified combed cotton fiber has a large number of anionic groups such as carboxymethyl and hydroxyl groups, giving the modified combed cotton fiber a strong adsorption capacity for the modified viscose fiber. The modified viscose fiber and modified combed cotton fiber are then processed into a blended yarn using Sirospinning technology. The modified viscose fiber and modified combed cotton fiber are bonded together through electrostatic self-assembly. The resulting blended yarn has good tensile and tear resistance and good antibacterial effect, but its antistatic properties and washability are still insufficient. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the purpose of this invention is to provide a high-performance silk / lyocell fiber blended fabric and its preparation method.

[0005] To achieve the above objectives, the present invention provides the following technical solution: A high-performance silk / lyocell blended fabric comprising the following raw materials in parts by weight: 25-35 parts silk fiber, 65-75 parts lyocell fiber, 10-15 parts antibacterial and antistatic composite functional additives, 10-20 parts crosslinking agent, 15-20 parts softener, and 900-1100 parts deionized water; The antibacterial and antistatic composite functional additive is prepared by the following method: S1: Triphenylphosphine reacts with 2-(chloromethyl)-2-(hydroxymethyl)propane-1,3-diol to generate intermediate 1; the reaction equation is shown below: S2: Intermediate 1 reacts with 6-(acryloyloxy)hexanoic acid to generate intermediate 2; the reaction equation is shown below: S3: Intermediate 2 reacts with 1-methyl-3-(3-aminopropyl)-3-chloroimidazolium to generate intermediate 3, and the reaction equation is shown below: S4: Intermediate 3 reacts with 2-(2,5,8,11-tetraoxadodecyl)ethylene oxide to generate an antibacterial and antistatic composite functional additive. The reaction equation is shown below:

[0006] In step S1, the molar ratio of triphenylphosphine to 2-(chloromethyl)-2-(hydroxymethyl)propane-1,3-diol is 1:(1.02-1.04).

[0007] In step S2, the molar ratio of intermediate 1 to 6-(acryloyloxy)hexanoic acid is 1:(3.03-3.05).

[0008] In step S3, the molar ratio of intermediate 2 to 1-methyl-3-(3-aminopropyl)-3-chloroimidazolium is 1:(3.01-3.02).

[0009] In step S4, the molar ratio of intermediate 3 to 2-(2,5,8,11-tetraoxadodecyl)ethylene oxide is 1:(3.01-3.03).

[0010] The crosslinking agent is prepared by the following method: N1: 4,4'-Diaminodiphenyl ether reacts with trans-9,10-epoxyoctadecanoic acid to generate intermediate A; the reaction equation is shown below: N2: Intermediate A reacts with epichlorohydrin to form a crosslinking agent. The reaction equation is shown below:

[0011] In step N1, the molar ratio of 4,4'-diaminodiphenyl ether to trans-9,10-epoxyoctadecanoic acid is 1:2.01.

[0012] In step N2, the molar ratio of intermediate A to epichlorohydrin is 1:2.03.

[0013] The softener is an organosilicone microemulsion softener.

[0014] A method for preparing a high-performance silk / lyocell blended fabric includes the following steps: (1) Weigh out the following by weight: 25-35 parts of silk fiber, 65-75 parts of lyocell fiber, 10-15 parts of antibacterial and antistatic composite functional additives, 10-20 parts of crosslinking agent, 15-20 parts of softener, and 900-1100 parts of deionized water. (2) Open the silk fiber and lyocell fiber respectively, spin the two fibers after opening to obtain blended yarn; weave the blended yarn into greige fabric; (3) Stir and mix the antibacterial and antistatic composite functional additives, crosslinking agent, softener and deionized water to obtain the finishing solution; (4) The greige fabric is immersed in the finishing solution, and after ultrasonication, soaking and drying, a high-performance silk fiber / lyocell fiber blended fabric is obtained.

[0015] Due to the adoption of the above technical solutions, the beneficial effects of the present invention include: The silk / lyocell blended fabric prepared by this invention exhibits excellent mechanical properties, washability, antistatic properties, and antibacterial properties. The antibacterial and antistatic composite functional additives added to the components of the blended fabric enhance the fabric's antibacterial and antistatic properties through the synergistic effect of quaternary phosphonium salt cationic structure, imidazolium cationic structure, flexible ether chain, and hydroxyl groups. The added crosslinking agent molecules significantly improve the fabric's mechanical properties and washability through the synergistic effect of diphenyl ether structure, epoxy groups, hydroxyl groups, carboxyl groups, and long-chain alkyl flexible segments. Attached Figure Description

[0016] Figure 1 The nuclear magnetic resonance hydrogen spectrum of the antibacterial and antistatic composite functional additive prepared in Example 1.

[0017] Figure 2 The high-resolution mass spectrum of the antibacterial and antistatic composite functional additive prepared in Example 1 is shown.

[0018] Figure 3 The image shows the proton NMR spectrum of the crosslinking agent prepared in Example 4.

[0019] Figure 4 The image shows a high-resolution mass spectrum of the crosslinking agent prepared in Example 4. Detailed Implementation

[0020] The following description, in conjunction with specific embodiments, provides further details, but the present invention is not limited to these embodiments.

[0021] Example 1: Preparation of antibacterial and antistatic composite functional additives S1: 300 ml of anhydrous acetonitrile, 0.1 mol of triphenylphosphine, and 0.102 mol of 2-(chloromethyl)-2-(hydroxymethyl)propane-1,3-diol were stirred and mixed, and the mixture was refluxed for 24 h. After cooling to room temperature, 350 ml of cold diethyl ether was added and stirred to precipitate the product. The product was filtered, and the filter cake was washed with cold diethyl ether (3 × 50 ml). The product was then dried under vacuum at 60 °C for 12 h to obtain intermediate 1. Its 1H NMR data are as follows: 1 H NMR (400 MHz, DMSO-) d 6 ) δ 7.90-7.82 (m, 6H), 7.78-7.69 (m, 3H), 7.66-7.57 (m, 6H), 4.65 (m, 3H), 3.87 (t, J = 6.1 Hz, 2H), 3.58-3.43 (m, 6H); HRMS (m / z):381.1619[M-Cl] + ; S2: Under nitrogen protection, 800 ml of anhydrous tetrahydrofuran and 0.303 mol of 6-(acryloyloxy)hexanoic acid were stirred and mixed. Then, 0.31 mol of dicyclohexylcarbodiimide and 0.06 mol of 4-dimethylaminopyridine were added, and the mixture was stirred for 15 min. 0.1 mol of intermediate 1 was added, and the reaction was carried out at 25 °C for 18 h. After filtration, the mixture was distilled under reduced pressure at 40 °C for 1 h. The crude product was purified by silica gel column chromatography (V... 二氯甲烷 :V 甲醇 The ratio of crude oil to distillate was 5:1. The intermediate was distilled under reduced pressure at 40℃ for 1 hour to obtain intermediate 2. Its 1H NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d)δ 7.86-7.77 (m, 6H), 7.66-7.57 (m, 9H), 6.13 (d, J = 12.4 Hz, 3H), 6.06 (m,3H), 5.95 (d, J = 12.4 Hz, 3H), 4.23 (d, J = 13.3 Hz, 12H), 4.09 (m, 2H), 2.29 (m, 6H), 1.63 (d, J = 12.1 Hz, 12H), 1.41 (t, J = 6.2 Hz, 6H); HRMS (m / z):885.3978[M-Cl] + ; S3: Under nitrogen protection, 700 ml of anhydrous acetonitrile, 0.1 mol of intermediate 2, and 0.301 mol of 1-methyl-3-(3-aminopropyl)-3-chloroimidazolium were stirred and mixed. 0.03 mol of triethylamine was added, and the mixture was heated to 50 °C and reacted for 8 h. After cooling to room temperature, the mixture was filtered. The filtrate was distilled under reduced pressure at 50 °C for 1 h. 400 ml of cold n-hexane was added and stirred to precipitate the precipitate. The precipitate was filtered, and the filter cake was washed successively with cold n-hexane (3 × 50 ml) and cold diethyl ether (2 × 50 ml). The mixture was then dried under vacuum at 50 °C for 10 h to obtain intermediate 3. Its 1H NMR data are as follows: 1 H NMR (400 MHz, DMSO- d 6 ) δ 9.54 (s, 3H), 8.00 (m, 3H), 7.86-7.77 (m, 6H), 7.65-7.57 (m, 9H), 7.50 (m, 3H), 4.39 (m, 6H), 4.29 (m, 6H), 4.11 (d, J =10.9 Hz, 8H), 3.90 (s, 9H), 3.59-3.54 (m, 3H), 2.81 (dd, J = 2.2, 4.5 Hz,12H), 2.40 (m, 6H), 2.27 (d, J = 9.9 Hz, 12H), 1.64 (m, 12H), 1.41 (t, J =6.2 Hz, 6H); HRMS (m / z): 326.4385 [M-4Cl] 4+ ; S4: Under nitrogen protection, 800 ml of anhydrous ethanol, 0.1 mol of intermediate 3, 0.301 mol of 2-(2,5,8,11-tetraoxadodecyl)ethylene oxide, and 0.03 mol of triethylamine were stirred and mixed. The mixture was heated to 60 °C and reacted for 8 h. After cooling to room temperature, the mixture was filtered and distilled under reduced pressure at 50 °C for 1 h. The distillate was then distilled using a mixture of 650 ml of ethyl acetate and anhydrous ethanol (V...乙酸乙酯 :V 无水乙醇 The mixture was recrystallized at a ratio of 8:2 and dried under vacuum at 50°C for 8 hours to obtain an antibacterial and antistatic composite functional additive; its proton nuclear magnetic resonance spectrum is shown below. Figure 1 As shown, the proton NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 9.54 (s, 3H), 8.00 (m, 3H), 7.86-7.77 (m,6H), 7.65-7.57 (m, 9H), 7.50 (m, 3H), 4.49-4.37 (m, 6H), 4.29 (t, J = 6.0 Hz,6H), 4.15-4.04 (m, 8H), 3.91 (d, J = 5.0 Hz, 3H), 3.90 (s, 9H), 3.65-3.44 (m,42H), 3.41 (s, 3H), 3.32 (s, 9H), 2.92-2.68 (m, 9H), 2.66-2.57 (m, 9H), 2.41-2.23 (m, 18H), 1.63 (d, J = 8.8 Hz, 12H), 1.41 (t, J = 6.2 Hz, 6H); its high-resolution mass spectrum is as follows: Figure 2 As shown, the mass spectrometry data are as follows: HRMS (m / z): 491.7876 [M-4Cl] 4+ .

[0022] Example 2: Preparation of antibacterial and antistatic composite functional additives S1: Mix 300 ml of anhydrous acetonitrile, 0.1 mol of triphenylphosphine, and 0.103 mol of 2-(chloromethyl)-2-(hydroxymethyl)propane-1,3-diol under stirring and reflux for 24 h. Cool to room temperature, add 350 ml of cold diethyl ether and stir to precipitate. Filter, wash the filter cake with cold diethyl ether (3 × 50 ml), and dry under vacuum at 60 °C for 12 h to obtain intermediate 1; S2: Under nitrogen protection, 800 ml of anhydrous tetrahydrofuran and 0.304 mol of 6-(acryloyloxy)hexanoic acid were stirred and mixed. Then, 0.31 mol of dicyclohexylcarbodiimide and 0.06 mol of 4-dimethylaminopyridine were added, and the mixture was stirred for 15 min. 0.1 mol of intermediate 1 was added, and the reaction was carried out at 25 °C for 18 h. After filtration, the mixture was distilled under reduced pressure at 40 °C for 1 h. The crude product was purified by silica gel column chromatography (V... 二氯甲烷 :V 甲醇 The ratio of the distillate to the intermediate was 5:1. The intermediate was distilled under reduced pressure at 40°C for 1 hour to obtain intermediate 2. S3: Under nitrogen protection, 700 ml of anhydrous acetonitrile, 0.1 mol of intermediate 2, and 0.3015 mol of 1-methyl-3-(3-aminopropyl)-3-chloroimidazolium were stirred and mixed. 0.03 mol of triethylamine was added, and the mixture was heated to 55 °C and reacted for 7 h. After cooling to room temperature, the mixture was filtered, and the filtrate was distilled under reduced pressure at 50 °C for 1 h. 400 ml of cold n-hexane was added and stirred to precipitate the precipitate. The precipitate was filtered, and the filter cake was washed successively with cold n-hexane (3 × 50 ml) and cold diethyl ether (2 × 50 ml). The mixture was then dried under vacuum at 50 °C for 10 h to obtain intermediate 3. S4: Under nitrogen protection, 800 ml of anhydrous ethanol, 0.1 mol of intermediate 3, 0.302 mol of 2-(2,5,8,11-tetraoxadodecyl)ethylene oxide, and 0.03 mol of triethylamine were stirred and mixed. The mixture was heated to 65 °C and reacted for 7 h. After cooling to room temperature, the mixture was filtered and distilled under reduced pressure at 50 °C for 1 h. The distillate was then distilled using a mixture of 650 ml of ethyl acetate and anhydrous ethanol (V... 乙酸乙酯 :V 无水乙醇 The mixture of 8:2 was recrystallized and dried under vacuum at 50°C for 8 hours to obtain an antibacterial and antistatic composite functional additive.

[0023] Example 3: Preparation of antibacterial and antistatic composite functional additives S1: 300 ml of anhydrous acetonitrile, 0.1 mol of triphenylphosphine, and 0.104 mol of 2-(chloromethyl)-2-(hydroxymethyl)propane-1,3-diol were stirred and mixed, and the mixture was refluxed for 24 h. After cooling to room temperature, 350 ml of cold diethyl ether was added and stirred to precipitate the product. The product was filtered, and the filter cake was washed with cold diethyl ether (3 × 50 ml). The product was then dried under vacuum at 60 °C for 12 h to obtain intermediate 1. S2: Under nitrogen protection, 800 ml of anhydrous tetrahydrofuran and 0.305 mol of 6-(acryloyloxy)hexanoic acid were stirred and mixed. Then, 0.31 mol of dicyclohexylcarbodiimide and 0.06 mol of 4-dimethylaminopyridine were added, and the mixture was stirred for 15 min. 0.1 mol of intermediate 1 was added, and the reaction was carried out at 30 °C for 17 h. After filtration, the mixture was distilled under reduced pressure at 40 °C for 1 h. The crude product was purified by silica gel column chromatography (V... 二氯甲烷 :V 甲醇 The ratio of the distillate to the intermediate was 5:1. The intermediate was distilled under reduced pressure at 40°C for 1 hour to obtain intermediate 2. S3: Under nitrogen protection, 700 ml of anhydrous acetonitrile, 0.1 mol of intermediate 2, and 0.302 mol of 1-methyl-3-(3-aminopropyl)-3-chloroimidazolium were stirred and mixed. 0.03 mol of triethylamine was added, and the mixture was heated to 60 °C and reacted for 6 h. After cooling to room temperature, the mixture was filtered, and the filtrate was distilled under reduced pressure at 50 °C for 1 h. 400 ml of cold n-hexane was added and stirred to precipitate the precipitate. The precipitate was filtered, and the filter cake was washed successively with cold n-hexane (3 × 50 ml) and cold diethyl ether (2 × 50 ml). The mixture was then dried under vacuum at 50 °C for 10 h to obtain intermediate 3. S4: Under nitrogen protection, 800 ml of anhydrous ethanol, 0.1 mol of intermediate 3, 0.303 mol of 2-(2,5,8,11-tetraoxadodecyl)ethylene oxide, and 0.03 mol of triethylamine were stirred and mixed. The mixture was heated to 70 °C and reacted for 6 h. After cooling to room temperature, the mixture was filtered and distilled under reduced pressure at 50 °C for 1 h. The distillate was then distilled using a mixture of 650 ml of ethyl acetate and anhydrous ethanol (V... 乙酸乙酯 :V 无水乙醇 The mixture of 8:2 was recrystallized and dried under vacuum at 50°C for 8 hours to obtain an antibacterial and antistatic composite functional additive.

[0024] Example 4 Preparation of crosslinking agent N1: Under nitrogen protection, 450 ml of anhydrous ethanol, 0.1 mol of 4,4'-diaminodiphenyl ether, 0.201 mol of trans-9,10-epoxyoctadecanoic acid, and 0.205 mol of triethylamine were stirred and mixed. The mixture was heated to 60 °C and reacted for 6 h. After cooling to room temperature, the mixture was filtered and distilled under reduced pressure at 50 °C for 1 h. 350 ml of cold n-hexane was added and stirred to precipitate the product. The precipitate was filtered, washed with cold n-hexane (3 × 50 ml), and dried under vacuum at 50 °C for 8 h to obtain intermediate A. Its 1H NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d )δ 11.47 (s, 2H), 6.90-6.82 (m, 4H), 6.72-6.65 (m, 4H), 4.41 (d, J = 3.6 Hz, 2H), 3.74 (d, J = 4.9 Hz, 2H), 3.66 (d, J = 4.9 Hz, 2H), 3.40 (d, J = 3.5 Hz, 2H), 2.25 (d, J = 4.7 Hz, 4H), 1.66-1.25 (m, 52H), 0.90 (t, J = 6.2 Hz, 6H); HRMS (m / z):797.5971[M+H] + ; Under nitrogen protection, 450 ml of anhydrous DMF, 0.1 mol of intermediate A, 0.203 mol of epichlorohydrin, and 2 mmol of tetrabutylammonium bromide were stirred and mixed thoroughly. The mixture was reacted at 70 °C for 8 h, then cooled to 30 °C. 40 g of 20 wt% sodium hydroxide solution was slowly added dropwise over 20 min, and the reaction was continued for 12 h. The reaction solution was diluted with 150 ml of deionized water and extracted with ethyl acetate (2 × 300 ml). The organic phases were combined and washed successively with 120 ml of deionized water and 120 ml of saturated brine. The mixture was dried over 30 g of anhydrous magnesium sulfate, filtered, and distilled under reduced pressure at 60 °C for 1 h. The purified solution was then purified by silica gel column chromatography (V). 乙酸乙酯 :V 石油醚=1:2), distilled under reduced pressure at 40℃ for 1 h, and dried under vacuum at 50℃ for 12 h to obtain the crosslinking agent; its proton NMR spectrum is shown below. Figure 3 As shown, the proton NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d δ 11.47 (s, 2H), 7.00-6.92 (m, 4H), 6.92-6.85 (m, 4H), 3.83 (d, J = 5.0 Hz, 2H), 3.69 (m, 2H), 3.58 (d, J = 4.9 Hz, 2H), 3.45-3.37 (m, 4H), 3.24 (d, J = 12.4 Hz, 2H), 2.96-2.84 (m, 4H), 2.25 (d, J = 4.7 Hz, 4H), 1.70-1.23 (m, 52H), 0.90 (t, J = 6.2 Hz, 6H); its high-resolution mass spectrum is shown below. Figure 4 As shown, the mass spectrometry data are as follows: HRMS (m / z): 909.6497 [M+H] + .

[0025] Example 5: Preparation of high-performance silk / lyocell fiber blended fabric (1) Weigh the following by weight: 250g of silk fiber (silkworm fiber), 650g of lyocell fiber, 100g of antibacterial and antistatic composite functional additive (prepared in Example 1), 100g of crosslinking agent (prepared in Example 4), 150g of softener (organic silicone microemulsion softener), and 9000g of deionized water; (2) Silk fibers and Lyocell fibers are fed into an opening machine and opened at a speed of 220 rpm. The two fibers after opening are put into a blending machine and mixed at 80 rpm for 15 min. Then, Siro spinning is carried out, with the spinning speed set at 1200 r / min and the twist at 450 twists / meter. After spinning, a blended yarn is obtained. The blended yarn is loaded into a 24 needle / inch double-sided circular knitting machine and the machine density is set at 56 rows / inch × 53 rows / inch to weave into a greige fabric. (3) Mix the antibacterial and antistatic composite functional additives, crosslinking agents, softeners and deionized water, and stir at 200 rpm for 10 min to obtain the finishing solution; (4) Immerse the fabric in the finishing solution and sonicate (ultrasonic frequency of 40kHz, ultrasonic power of 100W, ultrasonic time of 10min), soak at 40℃ for 1h, take it out and dry it in an oven at 60℃ for 12h to obtain a high-performance silk fiber / lyocell fiber blended fabric.

[0026] Example 6 Preparation of high-performance silk / lyocell fiber blended fabric (1) Weigh the following by weight: 300g of silk fiber (silkworm fiber), 700g of lyocell fiber, 120g of antibacterial and antistatic composite functional additive (prepared in Example 2), 150g of crosslinking agent (prepared in Example 4), 180g of softener (organic silicone microemulsion softener), and 10000g of deionized water; (2) Silk fibers and Lyocell fibers are fed into an opening machine and opened at a speed of 220 rpm. The two fibers after opening are put into a blending machine and mixed at 80 rpm for 15 min. Then, Siro spinning is carried out, with the spinning speed set at 1200 r / min and the twist at 450 twists / meter. After spinning, a blended yarn is obtained. The blended yarn is loaded into a 24 needle / inch double-sided circular knitting machine and the machine density is set at 56 rows / inch × 53 rows / inch to weave into a greige fabric. (3) Mix the antibacterial and antistatic composite functional additives, crosslinking agents, softeners and deionized water, and stir at 200 rpm for 10 min to obtain the finishing solution; (4) Immerse the fabric in the finishing solution and sonicate (ultrasonic frequency of 40kHz, ultrasonic power of 100W, ultrasonic time of 10min), soak at 40℃ for 1h, take it out and dry it in an oven at 60℃ for 12h to obtain a high-performance silk fiber / lyocell fiber blended fabric.

[0027] Example 7 Preparation of high-performance silk / lyocell fiber blended fabric (1) Weigh the following by weight: 350g of silk fiber (silkworm fiber), 750g of lyocell fiber, 150g of antibacterial and antistatic composite functional additive (prepared in Example 3), 200g of crosslinking agent (prepared in Example 4), 200g of softener (organic silicone microemulsion softener), and 11000g of deionized water; (2) Silk fibers and Lyocell fibers are fed into an opening machine and opened at a speed of 220 rpm. The two fibers after opening are put into a blending machine and mixed at 80 rpm for 15 min. Then, Siro spinning is carried out, with the spinning speed set at 1200 r / min and the twist at 450 twists / meter. After spinning, a blended yarn is obtained. The blended yarn is loaded into a 24 needle / inch double-sided circular knitting machine and the machine density is set at 56 rows / inch × 53 rows / inch to weave into a greige fabric. (3) Mix the antibacterial and antistatic composite functional additives, crosslinking agents, softeners and deionized water, and stir at 200 rpm for 10 min to obtain the finishing solution; (4) Immerse the fabric in the finishing solution and sonicate (ultrasonic frequency of 40kHz, ultrasonic power of 100W, ultrasonic time of 10min), soak at 40℃ for 1h, take it out and dry it in an oven at 60℃ for 12h to obtain a high-performance silk fiber / lyocell fiber blended fabric.

[0028] Comparative Example 1 The raw material composition and preparation method of the high-performance silk / lyocell blended fabric are basically the same as those in Example 6, except that the antibacterial and antistatic composite functional additive is replaced with an equal weight of the antibacterial and antistatic composite functional additive prepared by the following method: The preparation method of the antibacterial and antistatic composite functional additive is basically the same as that in Example 2, except that 2-(chloromethyl)-2-(hydroxymethyl)propane-1,3-diol in step S1 is replaced with an equimolar amount of 3-chloro-1-propanol; the amount of 6-(acryloyloxy)hexanoic acid in step S2 is replaced with 0.104 mol; the amount of 1-methyl-3-(3-aminopropyl)-3-chloroimidazolium in step S3 is replaced with 0.1015 mol; and the amount of 2-(2,5,8,11-tetraoxadodecyl)ethylene oxide in step S4 is replaced with 0.102 mol.

[0029] Comparative Example 2 The raw material composition and preparation method of the high-performance silk / lyocell blended fabric are basically the same as those in Example 6, except that the antibacterial and antistatic composite functional additive is replaced with an equal weight of the antibacterial and antistatic composite functional additive prepared by the following method: A1: Under nitrogen protection, 750 ml of anhydrous tetrahydrofuran and 0.304 mol of 6-(acryloyloxy)hexanoic acid were stirred and mixed. Then, 0.31 mol of dicyclohexylcarbodiimide and 0.06 mol of 4-dimethylaminopyridine were added, and the mixture was stirred for 15 min. Then, 0.1 mol of trimethylolpropane was added, and the reaction was carried out at 25 °C for 18 h. After filtration, the mixture was distilled under reduced pressure at 40 °C for 1 h. The crude product was purified by silica gel column chromatography (V... 二氯甲烷 :V 甲醇 The ratio of the two solutions was 5:1), and the intermediate B was obtained by vacuum distillation at 40°C for 1 hour. A2: Under nitrogen protection, 700 ml of anhydrous acetonitrile, 0.1 mol of intermediate B, and 0.3015 mol of 1-methyl-3-(3-aminopropyl)-3-chloroimidazolium were stirred and mixed. 0.302 mol of triethylamine was added, and the mixture was heated to 55 °C and reacted for 7 h. After cooling to room temperature, the mixture was filtered, and the filtrate was distilled under reduced pressure at 50 °C for 1 h. 550 ml of cold n-hexane was added and stirred to precipitate the precipitate. The precipitate was filtered, and the filter cake was washed successively with cold n-hexane (3 × 50 ml) and cold diethyl ether (2 × 50 ml). The mixture was then dried under vacuum at 50 °C for 10 h to obtain intermediate C. A3: Under nitrogen protection, 850 ml of anhydrous ethanol, 0.1 mol of intermediate C, 0.302 mol of 2-(2,5,8,11-tetraoxadodecyl)ethylene oxide, and 0.03 mol of triethylamine were stirred and mixed. The mixture was heated to 65 °C and reacted for 7 h. After cooling to room temperature, the mixture was filtered and distilled under reduced pressure at 50 °C for 1 h. The distillate was then distilled using 800 ml of a mixture of ethyl acetate and anhydrous ethanol (V... 乙酸乙酯 :V 无水乙醇 The mixture of 8:2 was recrystallized and dried under vacuum at 50°C for 8 hours to obtain an antibacterial and antistatic composite functional additive.

[0030] Comparative Example 3 The raw material composition and preparation method of the high-performance silk / lyocell blended fabric are basically the same as those in Example 6, except that the antibacterial and antistatic composite functional additive is replaced with an equal weight of the antibacterial and antistatic composite functional additive prepared by the following method: The preparation method of the antibacterial and antistatic composite functional additive is basically the same as that in Example 2, except that 2-(2,5,8,11-tetraoxadodecyl) ethylene oxide in step S4 is replaced with an equimolar amount of 1,2-epoxydodecyl.

[0031] Comparative Example 4 The raw material composition and preparation method of the high-performance silk / lyocell blended fabric are basically the same as those in Example 6, except that the antibacterial and antistatic composite functional additive is replaced with an equal weight of the antibacterial and antistatic composite functional additive prepared by the following method: The preparation method of the antibacterial and antistatic composite functional additive is basically the same as that in Example 2, except that the amount of 2-(2,5,8,11-tetraoxadodecyl)ethylene oxide in step S4 is replaced with 0.202 mol.

[0032] Comparative Example 5 The raw material composition and preparation method of the high-performance silk / lyocell blended fabric are basically the same as those in Example 6, except that the crosslinking agent is replaced with an equal weight of a crosslinking agent prepared by the following method: The preparation method of the crosslinking agent is basically the same as that in Example 4, except that the 4,4'-diaminodiphenyl ether in step N1 is replaced with an equimolar amount of 4,4'-diaminodiphenylmethane.

[0033] Comparative Example 6 The raw material composition and preparation method of the high-performance silk / lyocell blended fabric are basically the same as those in Example 6, except that the crosslinking agent is replaced with an equal weight of a crosslinking agent prepared by the following method: The preparation method of the crosslinking agent is basically the same as that in Example 4, except that the trans-9,10-epoxyoctadecanoic acid in step N1 is replaced with an equimolar amount of 8-(2-oxacyclopropyl)octanoic acid (CAS No. 52703-79-4).

[0034] Comparative Example 7 The raw material composition and preparation method of the high-performance silk / lyocell blended fabric are basically the same as those in Example 6, except that the crosslinking agent is replaced with a mixture of 12g intermediate A (prepared in step N1 of Example 4) and 3g epichlorohydrin.

[0035] The silk fibers used in the embodiments and comparative examples of this application are silkworm silk fibers with a fineness of 1.33 dtex and a length of 38 mm; the lyocell fibers have a fineness of 1.33 dtex and a length of 38 mm; the silicone microemulsion softener is model FS-2900B, produced by Liaoning Hengxing Fine Chemical Co., Ltd.; and the CAS number of 2-(chloromethyl)-2-(hydroxymethyl)propane-1,3-diol is 2210-06-2.

[0036] The high-performance silk / lyocell blended fabrics prepared in Examples 5-7 and Comparative Examples 1-7 were tested, and the test results are shown in Table 1.

[0037] Mechanical property testing: The blended fabrics prepared in Examples 5-7 and Comparative Examples 1-7 were cut into samples with a size of 200mm×50mm. The elongation at break of the samples was tested according to GB / T 3923.1-2013 standard, and the tensile speed was 100mm / min.

[0038] Washability test: The blended fabrics prepared in Examples 5-7 and Comparative Examples 1-7 were cut into samples with a size of 500mm × 500mm. The samples were immersed in a neutral soap solution containing 2g / L, with a liquor ratio of 1:50, and washed at 40℃ for 30 minutes. After washing, the samples were removed and rinsed twice in deionized water, with a liquor ratio of 1:100, for 1 minute each time. After rinsing, the samples were dehydrated for 10 minutes and air-dried. This washing process was repeated 100 times. The wash resistance was then determined according to the formula... (A: Dimensional change rate after washing, %) Initial length / width of the sample, in mm; Calculate the dimensional change rate of the sample in the length and width directions respectively (length / width of the sample after treatment, mm).

[0039] Antistatic performance test: The blended fabrics prepared in Examples 5-7 and Comparative Examples 1-7 were cut into samples with a size of 250mm×300mm, and the surface charge density of the samples was tested according to the charge surface density (C method) in GB / T 12703-1991 standard.

[0040] Antibacterial performance test: The blended fabrics prepared in Examples 5-7 and Comparative Examples 1-7 were cut into uniform circular shapes (9 mm in diameter) and placed in capped glass bottles containing PBS buffer (0.1 M, pH=7.4). The bottles were autoclaved at 121°C for 15 min, cooled under ventilation, and then further sterilized by UV irradiation in a clean bench for 1 h. The tested bacterial strain was Staphylococcus aureus. Individual colonies were picked from the test strain and diluted with physiological saline to a bacterial concentration of 10. 8 CFU / ml. Drop 100 μl of bacterial suspension onto LB solid medium, spread the bacterial suspension evenly with a spreader, attach the cut-out test sample, seal, and place the petri dish in a 37℃ biochemical incubator for constant temperature incubation. After 24 hours, remove the petri dish to observe the bacterial growth on the medium and record the size of the inhibition zone.

[0041] Table 1 Performance Test Data As can be seen from Table 1, the blended fabrics prepared in Examples 5-7 of this application have excellent mechanical properties, washability, antistatic properties and antibacterial properties.

[0042] The antibacterial and antistatic composite functional additives added to the components of the blended fabrics prepared in Examples 5-7 of this application simultaneously contain quaternary phosphonium salt cationic structures, imidazolium cationic structures, flexible ether chains, and hydroxyl groups. The hydroxyl groups can form hydrogen bonds with the fibers, stably fixing the antibacterial and antistatic composite functional additive molecules to the surfaces of lyocell and silk fibers. The imidazolium cationic structure and the quaternary phosphonium salt cationic structure, as dual cationic functional centers, can electrostatically adsorb negatively charged phospholipids on the surface of bacterial cell membranes, disrupting the integrity and permeability of the cell membrane and causing leakage of cell contents, thereby achieving a highly efficient antibacterial effect. Simultaneously, the flexible ether chain and hydroxyl groups in the molecules form strongly hydrophilic units, adsorbing a large number of water molecules from the air through hydrogen bonds, constructing a continuous water film conductive channel on the fabric surface, and reducing surface resistance. Furthermore, the positive charges in the quaternary phosphonium salt and imidazolium cationic structures dissipate through ion migration, synergistically forming a "hygroscopic-ionic dual conductive pathway" with the water film conductivity, significantly improving antistatic performance. The synergistic effect of the structural units in the antibacterial and antistatic composite functional additive achieves a synergistic improvement in the antibacterial and antistatic properties of the blended fabric. The antibacterial and antistatic composite functional additive used in Comparative Example 2 lacks a quaternary phosphonium salt cationic structure, relying solely on the imidazolium cationic structure to electrostatically adsorb onto the negatively charged phospholipids on the bacterial cell membrane surface, resulting in a decreased ability to disrupt the cell membrane. It also relies solely on the positive charge of the imidazolium cationic structure for ion migration, leading to a weakened charge dissipation ability. Ultimately, this results in a reduction in both the antibacterial and antistatic properties of the prepared blended fabric.

[0043] In Examples 5-7 of this application, the crosslinking agent molecule added to the components for preparing blended fabrics is a multi-arm structure with a diphenyl ether structure at its center, connecting epoxy groups, long-chain alkyl groups, carboxyl groups, and hydroxyl groups. The benzene rings serve as a rigid supporting framework, providing high-modulus load transfer nodes for the crosslinking network. The two benzene rings are connected by ether bonds, giving the rigid framework a certain degree of molecular rotational freedom, ensuring mechanical reinforcement while preventing crosslinking embrittlement. Furthermore, the epoxy groups in the crosslinking agent molecule can react with the hydroxyl groups on the surface of lyocell fibers and the amino groups in silk fibers to form stable covalent bonds. The crosslinking agent is composed of several molecules. Carboxyl and hydroxyl groups form strong hydrogen bonds with fibers and antibacterial / antistatic composite functional additives, creating a multi-point crosslinking network. Long-chain alkyl groups, acting as flexible segments embedded in the crosslinking network, undergo conformational changes under external force or washing, absorbing stress and buffering inter-fiber displacement, thus reducing localized stress concentration in the crosslinking network. The flexible long chains and the aromatic rigid skeleton form a "rigid-flexible synergy" molecular structure, maintaining the stability of the crosslinking network during repeated washing, preventing fiber slippage or loss of functional additives, thereby significantly improving the fabric's wash resistance. The synergistic effect of the various structures within the crosslinking agent molecule significantly enhances the mechanical properties and wash resistance of the blended fabric. In Comparative Example 5, 4,4'-diaminodiphenyl ether was replaced with 4,4'-diaminodiphenylmethane when preparing the crosslinking agent. This resulted in the flexible ether linkage unit between the two benzene rings in the crosslinking agent molecule being replaced by a methylene linkage unit. This led to a decrease in the overall flexibility of the molecule and an increase in the rigidity of the crosslinking network. As a result, it was difficult to buffer the internal stress generated by the moisture absorption, expansion, and contraction of the fibers during the washing process, which led to a decrease in the wash resistance of the blended fabric. At the same time, the excessively high crosslinking rigidity restricted the extension and slippage of the fiber chain segments, making the fabric prone to stress concentration when stretched, which led to a decrease in the elongation at break.

[0044] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. However, any modifications, alterations, and variations made by those skilled in the art without departing from the scope of the present invention based on the disclosed technical content are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and variations made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the present invention.

Claims

1. A high-performance silk / lyocell blended fabric, characterized in that, The ingredients include the following parts by weight: 25-35 parts silk fiber, 65-75 parts lyocell fiber, 10-15 parts antibacterial and antistatic composite functional additives, 10-20 parts crosslinking agent, 15-20 parts softener, and 900-1100 parts deionized water; The antibacterial and antistatic composite functional additive is prepared by the following method: S1: Triphenylphosphine reacts with 2-(chloromethyl)-2-(hydroxymethyl)propane-1,3-diol to generate intermediate 1. S2: Intermediate 1 reacts with 6-(acryloyloxy)hexanoic acid to generate intermediate 2. S3: Intermediate 2 reacts with 1-methyl-3-(3-aminopropyl)-3-chloroimidazolium to generate intermediate 3. S4: Intermediate 3 reacts with 2-(2,5,8,11-tetraoxadodecyl)ethylene oxide to generate an antibacterial and antistatic composite functional additive.

2. The high-performance silk / lyocell blended fabric according to claim 1, characterized in that, In step S1, the molar ratio of triphenylphosphine to 2-(chloromethyl)-2-(hydroxymethyl)propane-1,3-diol is 1:(1.02-1.04).

3. The high-performance silk / lyocell blended fabric according to claim 1, characterized in that, In step S2, the molar ratio of intermediate 1 to 6-(acryloyloxy)hexanoic acid is 1:(3.03-3.05).

4. The high-performance silk / lyocell blended fabric according to claim 1, characterized in that, In step S3, the molar ratio of intermediate 2 to 1-methyl-3-(3-aminopropyl)-3-chloroimidazolium is 1:(3.01-3.02).

5. The high-performance silk / lyocell blended fabric according to claim 1, characterized in that, In step S4, the molar ratio of intermediate 3 to 2-(2,5,8,11-tetraoxadodecyl)ethylene oxide is 1:(3.01-3.03).

6. The high-performance silk / lyocell blended fabric according to claim 1, characterized in that, The crosslinking agent is prepared by the following method: N1: 4,4'-Diaminodiphenyl ether reacts with trans-9,10-epoxyoctadecanoic acid to generate intermediate A; N2: Intermediate A reacts with epichlorohydrin to generate a crosslinking agent.

7. The high-performance silk / lyocell blended fabric according to claim 6, characterized in that, In step N1, the molar ratio of 4,4'-diaminodiphenyl ether to trans-9,10-epoxyoctadecanoic acid is 1:2.

01.

8. The high-performance silk / lyocell blended fabric according to claim 6, characterized in that, In step N2, the molar ratio of intermediate A to epichlorohydrin is 1:2.

03.

9. The high-performance silk / lyocell blended fabric according to claim 1, characterized in that, The softener is an organosilicone microemulsion softener.

10. A method for preparing a high-performance silk / lyocell blended fabric according to any one of claims 1-9, characterized in that, Includes the following steps: (1) Weigh out the following by weight: 25-35 parts of silk fiber, 65-75 parts of lyocell fiber, 10-15 parts of antibacterial and antistatic composite functional additives, 10-20 parts of crosslinking agent, 15-20 parts of softener, and 900-1100 parts of deionized water. (2) Open the silk fiber and lyocell fiber respectively, spin the two fibers after opening to obtain blended yarn; weave the blended yarn into greige fabric; (3) Stir and mix the antibacterial and antistatic composite functional additives, crosslinking agent, softener and deionized water to obtain the finishing solution; (4) The greige fabric is immersed in the finishing solution, and after ultrasonication, soaking and drying, a high-performance silk fiber / lyocell fiber blended fabric is obtained.

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