Wool-based antibacterial and warm high-strength flame-retardant yarn and preparation method thereof

Abstract

The present application belongs to the technical field of textiles, and provides a wool-based bacteriostatic warm high-strength flame-retardant yarn and a preparation method thereof. First, a bifunctional crosslinking agent containing phosphorus-nitrogen flame-retardant units and terminal alkyne functional groups is prepared, and a sericin grafted chitosan derivative is independently prepared by an enzymatic reaction as a biological interface lubricant. Wool fibers are subjected to chemical reduction treatment, and then an inorganic functional network mainly composed of metal phytate is generated in situ in the activated fibers. Then, by using a thiol-alkyne click chemistry reaction initiated by light, the bifunctional crosslinking agent is covalently grafted to the thiol group of wool keratin to form a three-dimensional organic covalent network penetrating the fiber matrix. Finally, the fiber surface is finished with the biological interface lubricant, and the prepared yarn has excellent bacteriostatic property, warmth, high strength and flame retardancy.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of textiles, and relates to a wool-based antibacterial and warm high-strength flame-retardant yarn and a preparation method thereof. BACKGROUND

[0002] The inherent performance defects of wool fibers, due to their structure and chemical composition, have affected their application in some high-performance and functional fields. First, the mechanical properties of wool fibers are relatively low, especially in the wet state, and their strength and wear resistance are inferior to those of cotton, hemp and most synthetic fibers. To improve this problem, the traditional method usually adopts blending with high-strength synthetic fibers (such as nylon and polyester), but this sacrifices the natural properties, biodegradability, and unique touch and comfort of wool to some extent. Second, existing wool flame-retardant technologies mainly rely on post-finishing processes, such as treatment with halogen-, phosphorus-, nitrogen-, or metal hydroxide-containing flame retardants. However, halogen-containing flame retardants release toxic dioxins and corrosive gases when burned; traditional phosphorus-nitrogen-based flame retardants are applied to the surface of fibers through single-step padding-drying processes, and their binding force with the fibers is weak, resulting in poor wash resistance and easy loss of function; and metal hydroxide-based flame retardants require extremely high addition amounts to achieve the desired effect, which affects the hand feeling, drape, and wearing comfort of the fabric.

[0003] Furthermore, wool keratin is rich in nutrients and is prone to bacterial and microbial growth in a hot and humid environment, which not only produces odors but also may pose a threat to human health. Traditional antibacterial finishing often uses silver ions / nano-silver, quaternary ammonium salts, or organic antibacterial agents. These methods also face the problem of insufficient functional durability, as the antibacterial agents are easily lost after multiple washes. SUMMARY

[0004] In view of the deficiencies in the prior art, the purpose of the present application is to provide a wool-based antibacterial and warm high-strength flame-retardant yarn and a preparation method thereof. The wool is chemically activated and in-situ mineralized to construct an inorganic network, and then a self-made multifunctional crosslinking agent is covalently bonded using click chemistry to form an organic-inorganic interpenetrating network. The resulting yarn has excellent high strength, flame retardancy, and antibacterial properties, thus meeting the needs of actual production.

[0005] To achieve this purpose, the present application adopts the following technical solutions:

[0006] In a first aspect, the present application provides a preparation method of a wool-based antibacterial and warm high-strength flame-retardant yarn, which comprises:

[0007] S1, L-lysine, ammonium bicarbonate is dispersed in deionized water, 3-bromopropynyl is added to react to obtain N, N-dipropargyl lysine crude product, phosphorus oxychloride is dispersed in anhydrous acetonitrile, and aminoethanol acetonitrile solution is added to react to obtain cyclic phosphoramide flame retardant, N, N-dipropargyl lysine crude product and cyclic phosphoramide flame retardant are dispersed in anhydrous dimethylformamide, N, N'-dicyclohexyl carbodiimide and N-hydroxysuccinimide are added to obtain a bisalkynyl phosphoramide crosslinking agent;

[0008] S2, carboxymethyl chitosan and sericin are dispersed in phosphate buffer to obtain a substrate solution, glutamine transaminase is added to the substrate solution to react, and after the reaction is completed, the dialysis step is carried out in a dialysis bag to obtain a biological interfacial lubricant;

[0009] S3, L-cysteine methyl ester hydrochloride is dispersed in deionized water, the pH is adjusted to 8-9, wool is immersed in deionized water to react to obtain pretreated wool, the pretreated wool is immersed in a phytic acid permeation solution, and immediately after soaking, it is immersed in an arginine-zinc chelate mineralization solution to obtain mineralized wool;

[0010] S4, the bisalkynyl phosphoramide crosslinking agent and the photoinitiator are dispersed in a tert-butyl alcohol / water mixed solvent, the mineralized wool is immersed in the tert-butyl alcohol / water mixed solvent, and irradiated with a ultraviolet lamp to obtain functionalized wool, the biological interfacial lubricant is dispersed in deionized water to obtain finishing working solution, the functionalized wool is immersed in the finishing working solution to obtain liquid wool, and two-stage heat treatment is carried out, and through drawing, roving and spinning processes, a wool-based antibacterial and warm high-strength flame-retardant yarn is obtained.

[0011] Specifically includes:

[0012] A1, phytic acid is dispersed in deionized water to obtain a phytic acid permeation solution, L-arginine and zinc sulfate heptahydrate are dispersed in deionized water in sequence, and the pH is adjusted to 6.8-7.2 to obtain an arginine-zinc chelate mineralization solution;

[0013] S1, L-lysine, ammonium bicarbonate is dispersed in deionized water, 3-bromopropynyl is added under ice water bath condition, and stirred at room temperature to react to obtain N, N-dipropargyl lysine crude product, nitrogen is introduced, phosphorus oxychloride is dispersed in anhydrous acetonitrile, and aminoethanol acetonitrile solution is added under ice water bath condition, the temperature is adjusted to a first temperature, and refluxed to react to obtain a cyclic phosphoramide flame retardant, N, N-dipropargyl lysine crude product and cyclic phosphoramide flame retardant are dispersed in anhydrous dimethylformamide, N, N'-dicyclohexyl carbodiimide and N-hydroxysuccinimide are added under ice water bath condition and mixed uniformly, and stirred at room temperature to react, after the reaction is completed, filtration, rotary evaporation and purification are carried out to obtain a bisalkynyl phosphoramide crosslinking agent;

[0014] S2, dispersing carboxymethyl chitosan and sericin in phosphate buffer, adjusting the temperature to the second temperature, stirring in a water bath to obtain a substrate solution, adding transglutaminase to the substrate solution and continuing to stir at the second temperature, inactivating after the reaction is completed, transferring the reaction solution into a dialysis bag after it is cooled, placing the dialysis bag in deionized water for a dialysis step, freeze-drying the dialyzed reaction solution to obtain a biological interfacial lubricant;

[0015] S3, dispersing L-cysteine methyl ester hydrochloride in deionized water and adjusting the pH to 8-9 using a sodium carbonate solution, immersing the wool in deionized water, stirring at a third temperature, washing and spinning after the reaction is completed to obtain pretreated wool, immersing the pretreated wool in a phytic acid permeation solution, performing 3 vacuum-atmospheric pressure cycles and soaking at atmospheric pressure, controlling the pick-up rate after soaking and immediately immersing in an arginine-zinc chelate mineralization solution, soaking at room temperature, washing and drying to obtain mineralized wool;

[0016] S4, dispersing a bis-alkynyl phosphoramide crosslinking agent and a photoinitiator in a tert-butyl alcohol / water mixed solvent, immersing the mineralized wool in the tert-butyl alcohol / water mixed solvent, irradiating using a UV lamp, washing thoroughly and drying after the irradiation is completed to obtain functionalized wool, dispersing the biological interfacial lubricant in deionized water to obtain a finishing working solution, immersing the functionalized wool in the finishing working solution to obtain wool with liquid and performing two-stage heat treatment, obtaining a wool-based antibacterial and warm high-strength flame-retardant yarn through the processes of drawing, roving and spinning after natural cooling.

[0017] As a multidentate organic phosphoric compound, phytic acid contains multiple phosphate groups in its molecular structure, so it can not only serve as a phosphorus source for subsequent inorganic phase formation, but also has excellent metal ion chelating ability. The chemical mechanism of preparing the arginine-zinc chelate mineralization solution lies in that the side chain functional groups (such as guanidino and amino) of L-arginine are used as ligands to form stable coordination compounds with divalent zinc ions in zinc sulfate. In step S1, under alkaline conditions, the α- and ε-amino groups of L-lysine as nucleophiles undergo nucleophilic substitution reaction with 3-bromopropyne to generate N,N'-dialkynyl lysine, which introduces two terminal alkyne functional groups in the product molecule. Through the condensation reaction of phosphorus oxychloride and aminoethanol, a cyclic phosphoramide structure containing a phosphorus-nitrogen bond is constructed, which is a pre-designed flame-retardant functional unit. Finally, the coupling reaction mediated by N,N'-dicyclohexyl carbodiimide and N-hydroxysuccinimide activates the carboxyl group of N,N'-dialkynyl lysine into an NHS active ester, which reacts with the nucleophilic site on the cyclic phosphoramide flame retardant to form a stable amide bond, covalently connecting the flame-retardant functional unit to the carboxyl group of the dialkynyl lysine skeleton, providing a material basis for subsequent introduction of high strength and high flame retardancy.

[0018] The biological interface lubricant is prepared in step S2, and the chemical mechanism thereof is enzyme-catalyzed graft copolymerization. By using the high specificity of transglutaminase, the isopeptide bond is formed between the γ-amide group of the glutamine residue in the silk fibroin molecular chain and the primary amino group in the carboxymethyl chitosan molecular chain. The enzyme-catalyzed reaction generates a stable graft copolymer covalently connected by two biological polymers. In step S3, the wool is first subjected to reduction treatment. In the weak alkaline condition, L-cysteine methyl ester hydrochloride is used as a reducing agent to convert part of the disulfide bonds in the keratin that play a crosslinking role into a highly nucleophilic free thiol group through a thiol-disulfide exchange reaction, thereby prepositioning a large number of covalent anchor points for the click chemistry reaction in step S4. At the same time, the breaking of the disulfide bonds makes the supermolecular structure of keratin loose, thereby improving the porosity of the fiber. Subsequently, in-situ mineralization is performed. By vacuum infiltration, the phytic acid molecules are efficiently transported and adsorbed onto the protein network inside the fiber. Subsequently, the fiber is immersed in a solution of zinc ions chelated by arginine. Since the fiber is rich in phytate anions, the zinc ions slowly dissociated from the chelate will preferentially react with the phytic acid inside the fiber to generate zinc phytate particles of nanoscale size. The role of arginine here is that of a reaction rate regulator. By dynamic coordination equilibrium, the concentration of free zinc ions is controlled, thereby inhibiting the rapid and random deposition of particles on the surface of the fiber, and realizing the uniform construction of the inorganic functional phase inside the fiber.

[0019] The wool subjected to the mineralization treatment is immersed in a solution containing a diacetylenic phosphoramide crosslinking agent and a photoinitiator. Under ultraviolet light irradiation, the photoinitiator decomposes to generate active free radicals, which in turn initiate the thiol-yne click chemistry reaction. The thiol groups on the wool keratin react with the acetylenic groups of the crosslinking agent in a radical addition manner. Since the crosslinking agent molecule contains two acetylenic groups, it can react with different keratin molecular chains, thereby forming a three-dimensional covalent crosslinking network in the entire fiber matrix. The network fixes the phosphorus-nitrogen flame-retardant functional units in the form of covalent bonds, and physically embeds the inorganic phase generated in-situ, thereby forming an organic-inorganic interpenetrating network structure. Finally, the biological interface lubricant prepared in step S2 is applied to the surface of the fiber through the padding-curing process. The high-temperature condition promotes the esterification or amidation reaction between the finishing agent and the functional groups on the surface of the fiber, thereby forming a durable finishing layer.

[0020] As a preferred technical solution of the present application, in A1, the mass fraction of the phytic acid infiltration solution is 3-8 wt.%, for example, it can be 3.0 wt.%, 3.5 wt.%, 4.0 wt.%, 4.5 wt.%, 5.0 wt.%, 5.5 wt.%, 6.0 wt.%, 6.5 wt.%, 7.0 wt.%, 7.5 wt.% or 8.0 wt.%, but is not limited to the listed values. Other values not listed in the range are also applicable.

[0021] In some optional embodiments, the mass ratio of the L-arginine, zinc sulfate heptahydrate and deionized water is (28-42):(23-34.5):800, for example, it can be (28, 29.4, 30.8, 32.2, 33.6, 35.0, 36.4, 37.8, 39.2, 40.6 or 42):(23, 24.15, 25.3, 26.45, 27.6, 28.75, 29.9, 31.05, 32.2, 33.35 or 34.5):800, but not only limited to the listed values, other values not listed in the range are also applicable.

[0022] As a preferred technical solution of the present application, in S1, the mass-volume ratio of the L-lysine, ammonium bicarbonate, deionized water and 3-bromopropynyl is (14-15) g:(21-25) g:(450-550) mL:(25-26.8) g, for example, it can be (14.0, 14.1, 14.2, 14.3, 14.4, 14.5, 14.6, 14.7, 14.8, 14.9 or 15.0) g:(21, 21.4, 21.8, 22.2, 22.6, 23.0, 23.4, 23.8, 24.2, 24.6 or 25) g:(450, 460, 470, 480, 490, 500, 510, 520, 530, 540 or 550) mL:(25, 25.18, 25.36, 25.54, 25.72, 25.9, 26.08, 26.26, 26.44, 26.62 or 26.8) g, but not only limited to the listed values, other values not listed in the range are also applicable.

[0023] In some optional embodiments, the light-shielded stirring reaction time is 20-30h, for example, it can be 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h or 30h, but not only limited to the listed values, other values not listed in the range are also applicable.

[0024] In some alternative embodiments, the mass volume ratio of the phosphorus oxychloride, the anhydrous acetonitrile and the acetonitrile solution of aminoethanol is (15-16) g: (180-220) mL: (6-7) g, for example, can be (15.0, 15.1, 15.2, 15.3, 15.4, 15.5, 15.6, 15.7, 15.8, 15.9 or 16.0) g: (180, 184, 188, 192, 196, 200, 204, 208, 212, 216 or 220) mL: (6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9 or 7.0) g, but not only limited to the listed values, other values not listed in the range of values are also applicable.

[0025] In some alternative embodiments, the concentration of the acetonitrile solution of aminoethanol is 2M.

[0026] In some alternative embodiments, the first temperature is 75-85℃, for example, can be 75℃, 76℃, 77℃, 78℃, 79℃, 80℃, 81℃, 82℃, 83℃, 84℃ or 85℃, but not only limited to the listed values, other values not listed in the range of values are also applicable.

[0027] In some alternative embodiments, the time of the first temperature reflux reaction is 4-6h, for example, can be 4.0h, 4.2h, 4.4h, 4.6h, 4.8h, 5.0h, 5.2h, 5.4h, 5.6h, 5.8h or 6.0h, but not only limited to the listed values, other values not listed in the range of values are also applicable.

[0028] In some optional embodiments, the mass-volume ratio of the N,N-dipropargyl lysine crude product, the cyclic phosphoramidate flame retardant, the anhydrous dimethylformamide, the N,N'-dicyclohexyl carbodiimide and the N-hydroxysuccinimide is (18-20) g: (9.5-10.7) g: (280-320) mL: (18.2-24) g: (9.2-11.3) g, for example, can be (18.0, 18.2, 18.4, 18.6, 18.8, 19.0, 19.2, 19.4, 19.6, 19.8 or 20.0) g: (9.5, 9.62, 9.74, 9.86, 9.98, 10.1, 10.22, 10.34, 10.46, 10.58 or 10.7) g: (280, 284, 288, 292, 296, 300, 304, 308, 312, 316 or 320) mL: (18.2, 18.78, 19.36, 19.94, 20.52, 21.1, 21.68, 22.26, 22.84, 23.42 or 24) g: (9.2, 9.41, 9.62, 9.83, 10.04, 10.25, 10.46, 10.67, 10.88, 11.09 or 11.3) g, but not limited to the listed values, other values not listed in the range are also applicable.

[0029] In some optional embodiments, the stirring reaction time at room temperature is 40-50 h, for example, can be 40 h, 41 h, 42 h, 43 h, 44 h, 45 h, 46 h, 47 h, 48 h, 49 h or 50 h, but not limited to the listed values, other values not listed in the range are also applicable.

[0030] As a preferred technical solution of the present application, in S2, the mass-volume ratio of the carboxymethyl chitosan, sericin, phosphate buffer, and transglutaminase is (10-12) g: (4-6) g: (800-1000) mL: (0.03-0.075) g, for example, can be (10.0, 10.2, 10.4, 10.6, 10.8, 11.0, 11.2, 11.4, 11.6, 11.8 or 12.0) g: (4.0, 4.2, 4.4, 4.6, 4.8, 5.0, 5.2, 5.4, 5.6, 5.8 or 6.0) g: (800, 820, 840, 860, 880, 900, 920, 940, 960, 980 or 1000) mL: (0.03, 0.0345, 0.039, 0.0435, 0.048, 0.0525, 0.057, 0.0615, 0.066, 0.0705 or 0.075) g, but not limited to the listed values, other values not listed in the range are also applicable.

[0031] In some alternative embodiments, the phosphate buffer has a pH of 6.8-7.2, for example, it can be pH 6.8, 6.9, 7.0, 7.1 or 7.2, but not limited to the listed values, other values not listed in the range are also applicable.

[0032] In some alternative embodiments, the second temperature is 45-55℃, for example, it can be 45℃, 46℃, 47℃, 48℃, 49℃, 50℃, 51℃, 52℃, 53℃, 54℃ or 55℃, but not limited to the listed values, other values not listed in the range are also applicable.

[0033] In some alternative embodiments, the second temperature water bath stirring time is 0.5-1h, for example, it can be 0.5h, 0.55h, 0.6h, 0.65h, 0.7h, 0.75h, 0.8h, 0.85h, 0.9h, 0.95h or 1.0h, but not limited to the listed values, other values not listed in the range are also applicable.

[0034] In some alternative embodiments, the transglutaminase has an activity of >100 U / g.

[0035] In some alternative embodiments, the second temperature stirring reaction time is 5-8h, for example, it can be 5.0h, 5.3h, 5.6h, 5.9h, 6.2h, 6.5h, 6.8h, 7.1h, 7.4h, 7.7h or 8.0h, but not limited to the listed values, other values not listed in the range are also applicable.

[0036] In some alternative embodiments, the dialysis bag has a molecular weight cut-off of 3500-5000 Da, for example, it can be 3500 Da, 3650 Da, 3800 Da, 3950 Da, 4100 Da, 4250 Da, 4400 Da, 4550 Da, 4700 Da, 4850 Da or 5000 Da, but not limited to the listed values, other values not listed in the range are also applicable.

[0037] In some alternative embodiments, the dialysis step is to place the dialysis bag in deionized water, dialysis in an environment of 4-10℃ for 72 hours. The deionized water is replaced every 8 hours. For example, it can be: placing the dialysis bag in deionized water, dialysis in an environment of (4.0, 4.6, 5.2, 5.8, 6.4, 7.0, 7.6, 8.2, 8.8, 9.4 or 10.0)℃ for 72 hours, and the deionized water is replaced every 8 hours, but not limited to the listed values, other values not listed in the range are also applicable.

[0038] As a preferred technical solution of the present application, in S3, the mass ratio of L-cysteine methyl ester hydrochloride, deionized water and wool is (3-8): (2500-3500): 100, for example, it can be (3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5 or 8.0): (2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400 or 3500): 100, but not only limited to the listed values, other values not listed in this range are also applicable.

[0039] In some optional embodiments, the mass fraction of the sodium carbonate solution is 10wt.%.

[0040] In some optional embodiments, the wool is wool after scouring and carding procedures.

[0041] In some optional embodiments, the third temperature is 25-35℃, for example, it can be 25℃, 26℃, 27℃, 28℃, 29℃, 30℃, 31℃, 32℃, 33℃, 34℃ or 35℃, but not only limited to the listed values, other values not listed in this range are also applicable.

[0042] In some optional embodiments, the stirring reaction time at the third temperature is 1.5-3h, for example, it can be 1.5h, 1.65h, 1.8h, 1.95h, 2.1h, 2.25h, 2.4h, 2.55h, 2.7h, 2.85h or 3.0h, but not only limited to the listed values, other values not listed in this range are also applicable.

[0043] In some optional embodiments, the pickup of the pretreated wool is 80-90%, for example, it can be 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89% or 90%, but not only limited to the listed values, other values not listed in this range are also applicable.

[0044] In some optional embodiments, the soaking time under normal pressure is 0.8-1.5h, for example, it can be 0.8h, 0.87h, 0.94h, 1.01h, 1.08h, 1.15h, 1.22h, 1.29h, 1.36h, 1.43h or 1.5h, but not only limited to the listed values, other values not listed in this range are also applicable.

[0045] In some optional embodiments, the post-soaking control rolling rate is 90-110%, for example, it can be 90%, 92%, 94%, 96%, 98%, 100%, 102%, 104%, 106%, 108% or 110%, but not limited to the listed values, and other values not listed in the range are also applicable.

[0046] In some optional embodiments, the soaking time at room temperature is 3-5h, for example, it can be 3.0h, 3.2h, 3.4h, 3.6h, 3.8h, 4.0h, 4.2h, 4.4h, 4.6h, 4.8h or 5.0h, but not limited to the listed values, and other values not listed in the range are also applicable.

[0047] As a preferred technical solution of the present application, in S4, the mass ratio of the diacetylenic phosphoramidite crosslinking agent, the photoinitiator, the tert-butyl alcohol / water mixed solvent and the mineralized wool is (10-20):(0.2-1):(2500-3500):100, for example, it can be (10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20):(0.2, 0.28, 0.36, 0.44, 0.52, 0.6, 0.68, 0.76, 0.84, 0.92 or 1):(2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400 or 3500):100, but not limited to the listed values, and other values not listed in the range are also applicable.

[0048] In some optional embodiments, the photoinitiator is photoinitiator 2959.

[0049] In some optional embodiments, the volume ratio of tert-butyl alcohol to water in the tert-butyl alcohol / water mixed solvent is 6:4.

[0050] In some optional embodiments, the power of the ultraviolet lamp irradiation is 400-600 W, the distance between the ultraviolet lamp and the liquid surface of the tertiary butanol / water mixed solvent is 15-25 cm, and the irradiation time is 15-30 min, and the wool is turned over every 5 minutes during the irradiation, for example, the power can be (400, 420, 440, 460, 480, 500, 520, 540, 560, 580, or 600) W, the distance between the ultraviolet lamp and the liquid surface of the tertiary butanol / water mixed solvent can be (15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25) cm, the irradiation time can be (15, 16.5, 18, 19.5, 21, 22.5, 24, 25.5, 27, 28.5, or 30) min, and the wool is turned over every 5 minutes during the irradiation, but it is not limited to the listed values, and other values not listed in the range are also applicable.

[0051] In some optional embodiments, the concentration of the finishing working liquid is 1-3 g / L, for example, it can be 1.0 g / L, 1.2 g / L, 1.4 g / L, 1.6 g / L, 1.8 g / L, 2.0 g / L, 2.2 g / L, 2.4 g / L, 2.6 g / L, 2.8 g / L, or 3.0 g / L, but it is not limited to the listed values, and other values not listed in the range are also applicable.

[0052] In some optional embodiments, the pickup rate of the liquid wool is 80-90%, for example, it can be 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, or 90%, but it is not limited to the listed values, and other values not listed in the range are also applicable.

[0053] In some optional embodiments, the two-stage heat treatment is: treated at 75-85°C for 8-12 min, and then baked at 125-140°C for 2-3 min. For example, it can be: treated at (75, 76, 77, 78, 79, 80, 81, 82, 83, 84, or 85) °C for (8.0, 8.4, 8.8, 9.2, 9.6, 10.0, 10.4, 10.8, 11.2, 11.6, or 12.0) min, and then baked at (125, 126.5, 128, 129.5, 131, 132.5, 134, 135.5, 137, 138.5, or 140) °C for (2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0) min, but it is not limited to the listed values, and other values not listed in the range are also applicable.

[0054] In a second aspect, the present application provides a wool-based bacteriostatic and warm high-strength flame-retardant yarn prepared by the preparation method of the first aspect.

[0055] Compared with the prior art, the present application has the following beneficial effects: by chemically activating wool, then generating an inorganic functional network in situ in the fiber, and then covalently bonding a self-designed multifunctional crosslinking agent by click chemistry, an organic network interpenetrated with the inorganic network is constructed, and the mechanical enhancement, flame retardation and bacteriostatic function are deeply implanted in the fiber matrix through stable covalent bonds, thereby imparting the yarn with high strength, high-efficiency flame retardation and broad-spectrum bacteriostatic performance. DETAILED DESCRIPTION

[0056] The technical solutions of the present application will be described in detail below in combination with specific examples. The examples described herein are specific specific embodiments of the present application, which are used to illustrate the concept of the present application; these descriptions are all explanatory and exemplary, and should not be understood as limiting the embodiments of the present application and the protection scope of the present application. In addition to the examples described herein, those skilled in the art can also employ other technical solutions that are obvious based on the content disclosed in the claims and the description of the present application, which include technical solutions that make any obvious substitutions and modifications to the examples described herein.

[0057] The chemical reagents used in the examples and comparative examples of the present application are all commercially available products and are not subjected to any further purification treatment.

[0058] Example 1

[0059] The present example provides a wool-based bacteriostatic and warm high-strength flame-retardant yarn and a preparation method thereof, and the preparation method specifically comprises the following steps:

[0060] A1, disperse phytic acid in deionized water to obtain a phytic acid permeate solution with a mass fraction of 4wt.%, and then disperse 30g of L-arginine and 25g of zinc sulfate heptahydrate in 800g of deionized water in sequence, and adjust the pH to 6.9 to obtain an arginine-zinc chelate mineralization solution;

[0061] S1, 14.2 g of L-lysine, 22 g of ammonium bicarbonate were dispersed in 500 mL of deionized water, 26 g of 3-bromopropyne was added under ice water bath condition, and the reaction was stirred at room temperature for 22 h to obtain N,N-dipropargyl lysine crude product. Under nitrogen atmosphere, 15.2 g of phosphorus oxychloride was dispersed in 190 mL of anhydrous acetonitrile, 6.2 g of aminoethanol acetonitrile solution was added under ice water bath condition, the concentration of the aminoethanol acetonitrile solution was 2 M, the temperature was adjusted to 78 °C to reflux for 5 h to obtain a cyclic phosphoramidate flame retardant. 18.5 g of N,N-dipropargyl lysine crude product and 9.8 g of cyclic phosphoramidate flame retardant were dispersed in 290 mL of anhydrous dimethylformamide, 20 g of N,N'-dicyclohexylcarbodiimide and 9.5 g of N-hydroxysuccinimide were added under ice water bath condition and mixed uniformly, and the reaction was stirred at room temperature for 42 h. After the reaction was completed, filtration, rotary evaporation and purification were performed to obtain a bis-propargyl phosphoramidate crosslinking agent;

[0062] S2, 11 g of carboxymethyl chitosan and 5 g of sericin were dispersed in 900 mL of phosphate buffer, the pH of the phosphate buffer was 7.0, the temperature was adjusted to 50 °C water bath and stirred for 0.8 h to obtain a substrate solution. 0.04 g of glutamine transaminase with an activity of >100 U / g was added to the substrate solution and the reaction was continued at 50 °C for 6 h. After the reaction was completed, the temperature was increased to inactivate the enzyme. The reaction solution was cooled, transferred into a dialysis bag, and dialyzed in deionized water. The dialysis bag had a molecular weight cut-off of 4000 Da, and the dialysis was performed at 6 °C for 72 hours. The deionized water was replaced every 8 hours during the dialysis. The dialyzed reaction solution was freeze-dried to obtain a biological interfacial lubricant.

[0063] S3, 5 g of L-cysteine methyl ester hydrochloride was dispersed in 3000 g of deionized water, and the pH was adjusted to 8.5 using a 10 wt.% sodium carbonate solution. 100 g of wool was immersed in deionized water, the wool was subjected to scouring and combing processes, and the reaction was stirred at 30 °C for 2 h. After the reaction was completed, the wool was washed and dried to obtain pretreated wool with a pick-up rate of 85%. The pretreated wool was immersed in a phytic acid permeation solution, subjected to 3 cycles of vacuum-normal pressure, and immersed in the solution under normal pressure for 1.0 h. The pick-up rate was controlled to be 100% after immersion, and the wool was immediately immersed in an arginine-zinc chelate mineralization solution. The wool was immersed at room temperature for 4 h, washed, and dried to obtain mineralized wool.

[0064] S4, 15 g of the di-alkynyl phosphoramide crosslinker and 0.5 g of the photoinitiator 2959 were dispersed in 3000 g of a t-butyl alcohol / water mixed solvent, the volume ratio of t-butyl alcohol to water in the t-butyl alcohol / water mixed solvent was 6:4, 100 g of the mineralized wool was immersed in the t-butyl alcohol / water mixed solvent, and irradiated with a UV lamp, the power of the UV lamp irradiation was 500 W, the distance between the UV lamp and the liquid surface of the t-butyl alcohol / water mixed solvent was 20 cm, the irradiation time was 20 min, the wool was turned over every 5 min during the irradiation, after the irradiation, the wool was washed thoroughly and dried, to obtain functionalized wool, the bio-interface lubricant was dispersed in deionized water to obtain a finishing working solution with a concentration of 2 g / L, the functionalized wool was immersed in the finishing working solution to obtain liquid-carrying wool, and two-stage heat treatment was performed, the pick-up rate of the liquid-carrying wool was 85%, and the two-stage heat treatment was as follows: treatment at 80℃ for 10 min, and then baking at 130℃ for 2.5 min, after natural cooling, the wool was subjected to the processes of drawing, roving and spinning, to obtain the wool-based antibacterial and warm high-strength flame-retardant yarn.

[0065] Example 2

[0066] The present embodiment provides a wool-based antibacterial and warm high-strength flame-retardant yarn and a preparation method thereof, the preparation method specifically comprising the following steps:

[0067] A1, the phytic acid was dispersed in deionized water to obtain a phytic acid permeate with a mass fraction of 7 wt.%, 40 g of L-arginine and 32 g of zinc sulfate heptahydrate were successively dispersed in 800 g of deionized water, and the pH was adjusted to 7.1 to obtain an arginine-zinc chelate mineralization solution;

[0068] S1, 14.8 g of L-lysine, 24 g of ammonium bicarbonate were dispersed in 460 mL of deionized water, 28 g of 3-bromopropyne was added under ice water bath condition, and the reaction was stirred at room temperature for 28 h to obtain N,N-di-alkynyl lysine crude product, under nitrogen atmosphere, 15.8 g of phosphorus oxychloride was dispersed in 210 mL of anhydrous acetonitrile, 6.8 g of an aminoethanol acetonitrile solution with a concentration of 2 M was added under ice water bath condition, the temperature was adjusted to 82℃ for reflux reaction for 4.5 h to obtain a cyclic phosphoramide flame retardant, 19.5 g of N,N-di-alkynyl lysine crude product and 10.5 g of the cyclic phosphoramide flame retardant were dispersed in 310 mL of anhydrous dimethylformamide, 22 g of N,N'-dicyclohexyl carbodiimide and 10 g of N-hydroxysuccinimide were added under ice water bath condition and mixed uniformly, and the reaction was stirred at room temperature for 48 h, after the reaction, filtration, rotary evaporation and purification were performed to obtain a di-alkynyl phosphoramide crosslinker;

[0069] S2, 10.5 g of carboxymethyl chitosan and 4.5 g of sericin protein were dispersed in 850 mL of phosphate buffer with pH of 6.9, the temperature was adjusted to 48℃ water bath stirring for 0.6 h to obtain the substrate solution, 0.06 g of glutamine transaminase with activity >100 U / g was added to the substrate solution and the reaction was continued at 48℃ stirring for 7 h, after the reaction was completed, the temperature was raised for inactivation, the reaction solution was cooled and transferred into a dialysis bag, and the dialysis bag was placed in deionized water for dialysis, the dialysis bag had a molecular weight cut-off of 3800 Da, and the dialysis was carried out at 8℃ for 72 hours, during which the deionized water was replaced every 8 hours, the dialyzed reaction solution was freeze-dried to obtain a biological interfacial lubricant;

[0070] S3, 7 g of L-cysteine methyl ester hydrochloride was dispersed in 2800 g of deionized water, and the pH was adjusted to 8.2 using a 10 wt.% sodium carbonate solution, 100 g of wool was immersed in deionized water, the wool was refined and carded after the scouring and carding process, and the wool was stirred at 28℃ for 2.5 h, after the reaction was completed, the wool was washed and dried to obtain pretreated wool, the pick-up rate of the pretreated wool was 82%, the pretreated wool was immersed in a phytic acid permeation solution, and was subjected to 3 vacuum-normal pressure cycles and 1.2 h of soaking at normal pressure, the pick-up rate after soaking was controlled at 95%, and the wool was immediately immersed in an arginine-zinc chelate mineralization solution, and was soaked at room temperature for 3.5 h, and was washed and dried to obtain mineralized wool;

[0071] S4, 12 g of bis-alkynyl phosphoramide crosslinking agent and 0.3 g of photoinitiator 2959 were dispersed in 2800 g of t-butyl alcohol / water mixed solvent with a volume ratio of t-butyl alcohol to water of 6:4, 100 g of mineralized wool was immersed in the t-butyl alcohol / water mixed solvent, and was irradiated with a UV lamp with a power of 450 W, the distance between the UV lamp and the liquid surface of the t-butyl alcohol / water mixed solvent was 22 cm, the irradiation time was 25 min, and the wool was turned over every 5 min during irradiation, after irradiation, the wool was washed and dried to obtain functionalized wool, the biological interfacial lubricant was dispersed in deionized water to obtain a finishing working solution with a concentration of 1.5 g / L, the functionalized wool was immersed in the finishing working solution to obtain liquid-carrying wool with a pick-up rate of 82%, and was subjected to two-stage heat treatment, i.e., treatment at 78℃ for 11 min, and baking at 135℃ for 2.2 min, and after natural cooling, the wool was subjected to drawing, roving, and spinning processes to obtain wool-based antibacterial and warm high-strength flame-retardant yarn.

[0072] Example 3

[0073] The embodiment provides a wool-based bacteriostatic warm-keeping high-strength flame-retardant yarn and a preparation method thereof, and the preparation method specifically comprises the following steps.

[0074] A1, dispersing phytic acid in deionized water to obtain a phytic acid permeate with a mass fraction of 5.5 wt.%, dispersing 35 g of L-arginine and 28 g of zinc sulfate heptahydrate in 800 g of deionized water in sequence, and adjusting the pH to 7.0 to obtain an arginine-zinc chelate mineralization solution;

[0075] S1, dispersing 15 g of L-lysine and 25 g of ammonium bicarbonate in 540 mL of deionized water, adding 25.5 g of 3-bromopropyne under the condition of an ice water bath, stirring the reaction at room temperature for 25 h in the dark to obtain a crude N,N-dipropargyl lysine, in a nitrogen atmosphere, dispersing 15.5 g of phosphorus oxychloride in 200 mL of anhydrous acetonitrile, adding 6.5 g of an aminoethanol acetonitrile solution under the condition of an ice water bath, the concentration of the aminoethanol acetonitrile solution is 2M, adjusting the temperature to 80 DEG C to reflux for 5.5 h to obtain a cyclic phosphoramide flame retardant, dispersing 19 g of the crude N,N-dipropargyl lysine and 10.0 g of the cyclic phosphoramide flame retardant in 300 mL of anhydrous dimethylformamide, adding 21 g of N,N'-dicyclohexyl carbodiimide and 10.5 g of N-hydroxysuccinimide under the condition of an ice water bath and mixing uniformly, stirring the reaction at room temperature for 45 h, filtering, rotary evaporation and purification after the reaction is completed to obtain a bisalkynyl phosphoramide crosslinking agent;

[0076] S2, dispersing 12 g of carboxymethyl chitosan and 6 g of sericin protein in 980 mL of a phosphate buffer, the pH of the phosphate buffer is 7.2, adjusting the temperature to 52 DEG C to stir in a water bath for 0.9 h to obtain a substrate solution, adding 0.05 g of glutamine transaminase to the substrate solution and continuing to stir the reaction at 52 DEG C for 5.5 h, the activity of the glutamine transaminase is >100 U / g, inactivating after the reaction is completed, transferring the reaction liquid into a dialysis bag after the reaction liquid is cooled and inactivated, and placing the dialysis bag in deionized water to perform a dialysis step, the dialysis step is that the dialysis bag is placed in deionized water, the molecular weight cut-off of the dialysis bag is 4500 Da, dialysis is performed at an environment of 5 DEG C for 72 hours, deionized water is replaced every 8 hours during the dialysis, and the reaction liquid after dialysis is freeze-dried to obtain a biological interfacial lubricant;

[0077] S3, 6 g of L-cysteine methyl ester hydrochloride was dispersed in 3200 g of deionized water, and the pH was adjusted to 8.8 using a sodium carbonate solution with a mass fraction of 10 wt.%, 100 g of wool was immersed in deionized water, the wool was wool after scouring and carding process, the reaction was stirred at 32℃ for 1.8 h, after the reaction was completed, washing, drying, and the like were performed to obtain pretreated wool, the pick-up rate of the pretreated wool was 88%, the pretreated wool was immersed in a phytic acid permeation solution, 3 vacuum-atmospheric pressure cycles were performed, and soaking was performed at atmospheric pressure for 1.4 h, after soaking, the pick-up rate was controlled to be 105%, and immediately immersed in an arginine-zinc chelate mineralization solution, and soaked at room temperature for 4.5 h, and washing and drying were performed to obtain mineralized wool;

[0078] S4, 18 g of bis-alkynyl phosphoramide crosslinking agent and 0.8 g of photoinitiator 2959 were dispersed in 3200 g of t-butyl alcohol / water mixed solvent, the volume ratio of t-butyl alcohol to water in the t-butyl alcohol / water mixed solvent was 6:4, 100 g of mineralized wool was immersed in the t-butyl alcohol / water mixed solvent, and ultraviolet lamp irradiation was performed, the power of the ultraviolet lamp irradiation was 550 W, the distance between the ultraviolet lamp and the liquid surface of the t-butyl alcohol / water mixed solvent was 18 cm, the irradiation time was 28 min, the wool was turned over every 5 min during irradiation, after irradiation, washing and drying were performed, to obtain functionalized wool, the biological interfacial lubricant was dispersed in deionized water to obtain a finishing working solution with a concentration of 2.5 g / L, the functionalized wool was immersed in the finishing working solution to obtain liquid-carrying wool with a pick-up rate of 88%, and two-stage heat treatment was performed, the two-stage heat treatment was: at 82℃, for 9 min, then placed at 138℃, and baked for 2.8 min, after natural cooling, the wool was subjected to drawing, roving, and spinning processes to obtain wool-based antibacterial, warm-keeping, high-strength, and flame-retardant yarns.

[0079] Example 4

[0080] The present embodiment provides wool-based antibacterial, warm-keeping, high-strength, and flame-retardant yarns and a preparation method thereof, the preparation method specifically comprising the following steps:

[0081] A1, phytic acid was dispersed in deionized water to obtain a phytic acid permeation solution with a mass fraction of 8 wt.%, 42 g of L-arginine and 34.5 g of zinc sulfate heptahydrate were successively dispersed in 800 g of deionized water, and the pH was adjusted to 7.2 to obtain an arginine-zinc chelate mineralization solution;

[0082] S1, 14.5 g of L-lysine, 23 g of ammonium bicarbonate were dispersed in 480 mL of deionized water, 27 g of 3-bromopropyne was added under ice water bath condition, and the reaction was stirred at room temperature for 30 h to obtain N,N-dipropargyl lysine crude product, 16 g of phosphorus oxychloride was dispersed in 220 mL of anhydrous acetonitrile, 7 g of aminoethanol acetonitrile solution was added under ice water bath condition, the concentration of the aminoethanol acetonitrile solution was 2 M, the temperature was adjusted to 85 °C to reflux for 6 h to obtain a cyclic phosphoramide flame retardant, 20 g of N,N-dipropargyl lysine crude product and 10.7 g of cyclic phosphoramide flame retardant were dispersed in 320 mL of anhydrous dimethylformamide, 24 g of N,N'-dicyclohexyl carbodiimide and 11.3 g of N-hydroxysuccinimide were added under ice water bath condition and mixed uniformly, the reaction was stirred at room temperature for 50 h, after the reaction was completed, filtration, rotary evaporation and purification were performed to obtain a bis-propargyl phosphoramide crosslinking agent;

[0083] S2, 10 g of carboxymethyl chitosan and 4 g of sericin were dispersed in 800 mL of phosphate buffer, the pH of the phosphate buffer was 6.8, the temperature was adjusted to 45 °C water bath and stirred for 1 h to obtain a substrate solution, 0.075 g of glutamine transaminase was added to the substrate solution and the reaction was continued at 45 °C for 8 h, the activity of the glutamine transaminase was > 100 U / g, after the reaction was completed, the temperature was increased for inactivation, the reaction solution was cooled and transferred into a dialysis bag, the dialysis bag was placed in deionized water for dialysis, the dialysis bag had a molecular weight cut-off of 5000 Da, dialysis was carried out at 10 °C for 72 hours, and the deionized water was replaced every 8 hours during the dialysis, the dialyzed reaction solution was freeze-dried to obtain a biological interfacial lubricant;

[0084] S3, 8 g of L-cysteine methyl ester hydrochloride was dispersed in 3500 g of deionized water, and the pH was adjusted to 9 using a sodium carbonate solution, the mass fraction of the sodium carbonate solution was 10 wt.%, 100 g of wool was immersed in deionized water, the wool was wool after scouring and combing process, the reaction was stirred at 35 °C for 3 h, after the reaction was completed, the wool was washed and spun dry to obtain pretreated wool, the pick-up rate of the pretreated wool was 90%, the pretreated wool was immersed in a phytic acid permeation solution, 3 vacuum-normal pressure cycles were carried out, and the wool was soaked at normal pressure for 1.5 h, after soaking, the pick-up rate was controlled at 110%, and the wool was immediately immersed in an arginine-zinc chelate mineralization solution, and the wool was soaked at room temperature for 5 h, and then washed and dried to obtain mineralized wool;

[0085] S4, 20 g of diacetylenic phosphonamide crosslinking agent and 1 g of photoinitiator 2959 were dispersed in 3500 g of t-butyl alcohol / water mixed solvent with a volume ratio of 6:4, 100 g of mineralized wool was immersed in the t-butyl alcohol / water mixed solvent, and irradiated with a UV lamp with a power of 600 W, a distance of 15 cm between the UV lamp and the liquid surface, and a stirring time of 30 min, the wool was stirred every 5 min during the irradiation, after the irradiation, the wool was washed and dried, and the functionalized wool was obtained, the biological interfacial lubricant was dispersed in deionized water to obtain a finishing working solution with a concentration of 3 g / L, the functionalized wool was immersed in the finishing working solution to obtain liquid-containing wool, and two-stage heat treatment was performed, the pick-up rate of the liquid-containing wool was 90%, and the two-stage heat treatment was carried out at 85℃ for 12 min, and then at 140℃ for 3 min, and after natural cooling, the yarn was obtained through the processes of drawing, roving and spinning.

[0086] Comparative Example 1

[0087] The present comparative example provides a wool-based antibacterial and warm high-strength flame-retardant yarn and a preparation method thereof, which is different from Example 1 in that the mineralized wool treated by the S3 step in Example 1 is not treated by the S4 step, but the same amount of diacetylenic phosphonamide crosslinking agent and biological interfacial lubricant as in Example 1 are physically mixed to prepare a single finishing working solution, and the above mineralized wool is finished by one-step pad-dry-cure process, and this process does not use UV irradiation, and other process parameters and operating conditions are the same as those in Example 1.

[0088] Comparative Example 2

[0089] The present comparative example provides a wool-based antibacterial and warm high-strength flame-retardant yarn and a preparation method thereof, which is different from Example 1 in that the wool is not treated by the S3 step, but directly by the step S4, and other process parameters and operating conditions are the same as those in Example 1.

[0090] Comparative Example 3

[0091] The present comparative example provides a wool-based antibacterial and warm high-strength flame-retardant yarn and a preparation method thereof, which is different from Example 1 in that no diacetylenic phosphonamide crosslinking agent is added in S4, and other process parameters and operating conditions are the same as those in Example 1.

[0092] The wool-based antibacterial and warm high-strength flame-retardant yarns prepared in Examples 1-4 and Comparative Examples 1-3 were tested, the test method for breaking strength was GB / T 3916-2013, the test method for limiting oxygen index was GB / T 5454-1997, the test method for antibacterial rate was GB / T 20944.3-2008, and the test method for warmth retention was GB / T 11048-2018.

[0093] The test results are shown in Table 1.

[0094] Table 1 Test results of wool-based antibacterial and warm high-strength flame-retardant yarns in Example 1-Example 4 and Comparative Example 1-Comparative Example 3

[0095]

[0096] As shown in Table 1, compared with Example 1, the breaking strength, limiting oxygen index, antibacterial rate and warmth of Comparative Example 1 all decreased; the breaking strength, limiting oxygen index, antibacterial rate and warmth of Comparative Example 2 all decreased; the breaking strength, limiting oxygen index and warmth of Comparative Example 3 all decreased. In Comparative Example 1, the dip-dry-cure process was used for one-step finishing, and the process did not use ultraviolet lamp irradiation. The degree of chemical cross-linking of the diacetylenic phosphoramide cross-linking agent in the fiber was reduced, and more remained in the physical adsorption stage. Insufficient cross-linking reaction would lead to a decrease in fiber strength. At the same time, the flame-retardant functional groups contained in the diacetylenic phosphoramide cross-linking agent could not form stable chemical bonds with wool fibers and mineralization layers, and the flame-retardant performance was reduced. In Comparative Example 2, the wool was not treated, and the combination efficiency of mineralization and cross-linking agent was reduced, and the mechanical strength was reduced. Step S3 can help phytic acid and arginine-zinc chelate to better deposit or complex in the inside and outside of the fiber, improve the stability of the flame-retardant layer, and step S3 can increase the combination sites of wool and zinc ions, so the antibacterial rate is reduced. In Comparative Example 3, the diacetylenic phosphoramide cross-linking agent was not used, and a certain cross-linking network could not be formed in the fiber structure through chemical bonds, and the flame-retardant groups were also lacking, so the breaking strength and flame retardancy decreased.

[0097] The above merely provides a specific implementation of the present application, but the protection scope of the present application is not limited thereto. It should be understood by those skilled in the art that any changes or replacements within the technical scope disclosed by the present application can be easily conceived by those skilled in the art, and all such changes and replacements fall within the protection scope and disclosure scope of the present application.

Claims

1. A process for the preparation of wool based bacteriostatic, warm, high strength, flame retardant yarn characterized in that, The preparation method comprises: S1, dispersing L-lysine and ammonium bicarbonate in deionized water, adding 3-bromopropynyl to react to obtain N,N-dipropargyl lysine crude product, dispersing phosphorus oxychloride in anhydrous acetonitrile, adding an aminoethanol acetonitrile solution to react to obtain a cyclic phosphoramide flame retardant, dispersing N,N-dipropargyl lysine crude product and the cyclic phosphoramide flame retardant in anhydrous dimethylformamide, adding N,N'-dicyclohexyl carbodiimide and N-hydroxysuccinimide to obtain a bisalkynyl phosphoramide crosslinker; S2, dispersing carboxymethyl chitosan and sericin in a phosphate buffer to obtain a substrate solution, adding transglutaminase to the substrate solution to react, and then transferring the reaction solution into a dialysis bag to perform a dialysis step to obtain a biological interfacial lubricant; S3, dispersing L-cysteine methyl ester hydrochloride in deionized water, adjusting the pH to 8-9, immersing wool in deionized water to react to obtain pretreated wool, immersing the pretreated wool in a phytic acid permeation solution, and then immersing the wool in an arginine-zinc chelate mineralization solution immediately after soaking to obtain mineralized wool; S4, dispersing the bisalkynyl phosphoramide crosslinker and a photoinitiator in a tert-butyl alcohol / water mixed solvent, immersing the mineralized wool in the tert-butyl alcohol / water mixed solvent, and irradiating using an ultraviolet lamp to obtain functionalized wool, dispersing the biological interfacial lubricant in deionized water to obtain a finishing working solution, immersing the functionalized wool in the finishing working solution to obtain wool with liquid, and performing two-stage heat treatment, and then performing a drawing, a roving, and a spinning process to obtain a wool-based antibacterial and warm high-strength flame-retardant yarn.

2. A process for the preparation of wool based bacteriostatic warm high strength flame retardant yarn as claimed in claim 1 wherein, The preparation method of the phytic acid permeation solution and the arginine-zinc chelate mineralization solution comprises: A1, dispersing phytic acid in deionized water to obtain a phytic acid permeation solution, and dispersing L-arginine and zinc sulfate heptahydrate in deionized water in sequence, and adjusting the pH to 6.8-7.2 to obtain an arginine-zinc chelate mineralization solution.

3. A process for the preparation of wool based bacteriostatic warm high strength flame retardant yarn as claimed in claim 1 wherein, In S1: The mass / volume ratio of the L-lysine, ammonium bicarbonate, deionized water, and 3-bromopropynyl is (14-15) g:(21-25) g:(450-550) mL:(25-26.8) g; The mass / volume ratio of the phosphorus oxychloride, anhydrous acetonitrile, and the aminoethanol acetonitrile solution is (15-16) g:(180-220) mL:(6-7) g.

4. A process for the preparation of wool based bacteriostatic warm high strength flame retardant yarn as claimed in claim 1 wherein, In S1: The mass / volume ratio of the N,N-dipropargyl lysine crude product, the cyclic phosphoramide flame retardant, anhydrous dimethylformamide, N,N'-dicyclohexyl carbodiimide, and N-hydroxysuccinimide is (18-20) g:(9.5-10.7) g:(280-320) mL:(18.2-24) g:(9.2-11.3) g.

5. The process for the preparation of wool based bacteriostatic warm high strength flame resistant yarn as claimed in claim 1 wherein, In S2: The mass / volume ratio of the carboxymethyl chitosan, sericin, phosphate buffer, and transglutaminase is (10-12) g:(4-6) g:(800-1000) mL:(0.03-0.075) g; The dialysis step is to place the dialysis bag in deionized water, and dialysis is performed at an environment of 4-10°C for 72 hours, and the deionized water is replaced every 8 hours during the dialysis.

6. A process for the preparation of wool based bacteriostatic warm high strength flame resistant yarn as claimed in claim 1 wherein, In S3: The mass ratio of the L-cysteine methyl ester hydrochloride, deionized water and wool is (3-8):(2500-3500):

100.

7. A process for the preparation of wool based bacteriostatic warm high strength flame resistant yarn as claimed in claim 1 wherein, In S4: The mass ratio of the bis-alkynyl phosphoramide crosslinking agent, photoinitiator, tertiary butanol / water mixed solvent and mineralized wool is (10-20):(0.2-1):(2500-3500):

100.

8. A process for the preparation of wool based bacteriostatic warm high strength flame retardant yarn as claimed in claim 1 wherein, In S4: The power of the ultraviolet lamp irradiation is 400-600 W, the distance between the ultraviolet lamp and the surface of the tertiary butanol / water mixed solvent is 15-25 cm, the irradiation time is 15-30 min, and the wool is turned over every 5 minutes during the irradiation; The two-stage heat treatment is: at 75-85℃, for 8-12 min, and then placed at 125-140℃, and baked for 2-3 min.

9. A process for the preparation of wool based bacteriostatic warm high strength flame resistant yarn as claimed in claim 2, wherein, In A1: The mass fraction of the phytic acid permeation solution is 3-8 wt.%; The mass ratio of the L-arginine, zinc sulfate heptahydrate and deionized water is (28-42):(23-34.5):

800.

10. The wool-based antibacterial and warm high-strength flame-retardant yarn prepared by the preparation method according to any one of claims 1-9.

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