Modification method of warm-keeping anti-migration down feather fiber material

Abstract

The invention relates to a modification method of a warm-keeping anti-migration down feather fiber material, and belongs to the technical field of feather fiber treatment. Down feather is activated through sodium bicarbonate and fatty alcohol-polyoxyethylene ether, bottom layer anchoring and protection are carried out through PDA-PEI, dynamic covalent cross-linked network construction is carried out through a modification liquid I, and hydrophobic aerogel loading is carried out through a modification liquid II. The modified liquid I contains polyvinyl alcohol, borax, a water-based anionic aliphatic polyurethane resin dispersion, a BYK-349 surfactant, guar hydroxypropyltrimethyl ammonium chloride and the like; the modified liquid II is prepared from hydrophobic nano silicon dioxide aerogel powder, a KH550 silane coupling agent, a BYK-111 dispersing agent, polyether modified polydimethylsiloxane, cetyl phosphate, absolute ethyl alcohol, ammonia water and the like. A three-layer structure of bottom layer anchoring, middle buffering and surface layer dewatering is formed, and through cooperation of the three layers, the initial filling power retention rate is very high, heat and humidity resistance is achieved, the heat preservation performance is good, durability is good, and performance attenuation is slow.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of feather fiber processing, and particularly relates to a modification method of a warm-keeping and anti-migration down fiber material. BACKGROUND

[0002] Down fibers, as a natural warm-keeping material, are widely used in warm-keeping products such as down jackets, sleeping bags and quilts due to their excellent loftiness, warm-keeping property and lightweight characteristics. The warm-keeping principle mainly relies on the static air layer formed between the fibers, which achieves heat insulation by reducing air convection. The loftiness of down is the core index of determining the warm-keeping performance, that is, the higher the loftiness, the more air is locked between the fibers, and the better the warm-keeping effect.

[0003] However, there are two key defects in natural down fibers, which limit their application scenarios and service life: first, the stability of the warm-keeping performance is insufficient. The surface of down fibers is rich in protein components, which is easily affected by humidity. In a humid environment, the fibers will aggregate after absorbing moisture, resulting in a decrease in loftiness and a decrease in warm-keeping effect. In addition, the fiber structure is easily damaged during long-term use or washing, further weakening its warm-keeping durability. The second is the prominent problem of fiber migration. Down fibers have a small diameter (usually 5-20 μm) and a short length (mostly 1-3 cm), and the surface is smooth, so the friction with the fabric is small. During product use or washing, the fibers are easy to drill out of the fabric seams (i.e., the "drilling down" phenomenon), which not only affects the appearance and comfort of the product, but also causes the warm-keeping performance to decay due to fiber loss.

[0004] To solve the above problems, researchers have treated down fibers through physical, chemical or composite modification methods, aiming to improve their warm-keeping stability and anti-migration ability while retaining the excellent properties of natural down. The modification of down fibers needs to consider both "enhancing warm-keeping stability" and "inhibiting fiber migration", and the existing technologies mainly fall into the following three categories: (1) Changing the surface morphology or structure of down fibers through physical means to enhance their adhesion to the fabric and optimize the loftiness and shape retention of the fibers; including surface roughening treatment and fiber grafting or entanglement; (2) Reacting with active groups (such as amino groups and hydroxyl groups) on the surface of down fibers through chemical reagents to introduce functional groups or coatings, improving their moisture absorption performance and surface adhesion; (3) Combining the advantages of physical and chemical modification to achieve synergistic effect through multi-step treatment.

[0005] Although the existing modification methods of warm-keeping and anti-migration down fiber materials have made some progress, there are still some technical problems that need to be further improved or solved, mainly in the following two aspects: 1. Durability problem: The modified down fibers are generally present, and the durability of the modification effect is insufficient. For example, the down fibers treated by physical adhesion method have weak bonding force of flame-retardant components and poor water resistance, and the flame-retardant function is easily lost after multiple washes. Similarly, the anti-migration performance of some anti-migration treatments will decrease significantly after multiple washes or long-term use.

[0006] 2. Stability problem of modification effect: In the traditional down composite fabric, the surface of the filled down fiber is damaged when coating or surface modification is performed, which affects the warmth retention and leads to poor stability of the modification effect. At the same time, some modification methods may be greatly affected by environmental factors such as humidity and temperature, resulting in unstable modification effect. SUMMARY

[0007] In view of the problems of poor durability and insufficient environmental stability of the existing down fiber material modification, the present application provides a modification method for a warm and anti-migration down fiber material. The method forms a three-layer structure of "bottom anchoring-intermediate buffering-surface hydrophobicity" through four steps: bottom anchoring phenolic hydroxyl-amino covalent bonding fiber surface to ensure that the modified layer does not fall off; middle layer dynamic network PVA-WPU-Gu-Borax to build a tangled dynamic key energy consumption, the intermediate network provides self-repairing anti-migration ability; surface aerogel fixed SiO2aerogel-KH550 silane coupling agent to form Si-O-C covalent bond, the surface layer enhances the hydrophobicity and warmth retention. The three work together to keep the initial loft retention rate very high. In a humid and hot environment, due to the hydrophobicity and aerogel air locking effect, the loft retention rate is high, the durability is good, and the performance degradation is slow. The specific technical scheme is as follows: A modification method for a warm and anti-migration down fiber material, the modification method comprising the following steps: S1, activation: immersing the washed down into an aqueous solution containing sodium bicarbonate and fatty alcohol polyoxyethylene ether, washing, dehydrating, and obtaining activated down; S2, bottom anchoring and protection: preparing a pH 8.0-8.5 Tris-HCl buffer solution containing 2.0-2.5 g / L dopamine hydrochloride and 0.1-0.2 g / L polyethyleneimine to obtain a PDA-PEI solution; immersing the activated down into the PDA-PEI solution, oscillating treatment, washing, dehydrating, and air drying to obtain modified down A; S3, dynamic covalent cross-linking network construction: prepare an aqueous solution containing 3.0wt%-3.5wt% polyvinyl alcohol, 0.4wt%-0.6wt% borax, 8wt%-10wt% aqueous anionic aliphatic polyurethane resin dispersion, 0.1wt%-0.3wt% BYK-349 surfactant and 0.8wt%-1.5wt% guar gum hydroxypropyltrimethyl ammonium chloride, adjust to pH 9-9.5 to obtain modified liquid I; immerse the modified down A in the modified liquid I, vacuum to-0.05MPa--0.06MPa, 30rpm-50rpm stirring for 15min-20min, restore to normal pressure and keep stirring for 30min-40min, take out, drain, stand, solidify, air dry to obtain modified down B; S4, hydrophobic aerogel loading: prepare an aqueous suspension containing 5wt%-7wt% hydrophobic nanosilica aerogel powder, 0.5wt%-0.8wt% KH550 silane coupling agent, 0.05%-0.1% BYK-111 dispersant, 0.1wt%-0.2wt% polyether modified polydimethylsiloxane, 0.2wt%-0.5wt% cetyl alcohol phosphate, 20wt%-25wt% anhydrous ethanol, 5wt%-6wt% ammonia water (ammonia water concentration 25wt%-28wt%) to obtain modified liquid II; immerse the modified down B in the modified liquid II, vacuum to-0.05MPa--0.06MPa, 30rpm-50rpm stirring for 25min-35min, restore to normal pressure and keep stirring for 40min-50min, take out, drain, immerse in an aqueous solution containing 1wt%-1.2wt% acetic acid, stir, take out, drain; wash with deionized water for 2-3 times, centrifugal dewatering, air dry to obtain modified down C; S5, after performance balancing treatment of the modified down C, obtain the warm-keeping and anti-migration down fiber material.

[0008] In S1 of the above modification method, the activation is: immerse the washed down in an aqueous solution containing 0.5wt%-0.8wt% sodium bicarbonate and 1.0wt%-1.5wt% fatty alcohol polyoxyethylene ether, stirring at 40℃-45℃, 30rpm-50rpm for 20min-30min, wash with deionized water for 2-3 times, centrifugal dewatering, control the moisture content of 45wt%-50wt% to obtain the activated down.

[0009] In S1 of the modification method, the cleaning method of the washed down feather includes: using a water solution containing 0.3wt%-0.5wt% alkyl polysaccharide to clean the down feather at 30-35℃ for 30-50min with a bath ratio of 1kg:(40-50L), cleaning 3-4 times with deionized water at 30-35℃ until no foam and clear water, centrifugal dewatering, and controlling the water content to be less than or equal to 45%, to obtain the washed down feather.

[0010] The down feather is goose feather or duck feather.

[0011] In S2 of the modification method, the activated down feather is immersed in the PDA-PEI solution with a bath ratio of 1kg:(35-40L) and oscillated at 15-20℃ for 4-5h under an oxygen atmosphere, i.e. continuously supplying low flow rate air or oxygen of 0.8-1.2L / (min·kg down feather), cleaned 3-4 times with deionized water, centrifugal dewatered at 400-600rpm for 5-8min, and air dried at 50-55℃ for 1-1.5h, to obtain the modified down feather A.

[0012] In S3 of the modification method, the modified down feather A is immersed in the modified solution I with a bath ratio of 1kg:(25-30L), vacuumed to-0.05MPa to-0.06MPa, stirred at 30-50rpm for 15-20min, restored to normal pressure and stirred for 30-40min, taken out, drained until no continuous dripping, and placed at 85%-90%RH and 40-45℃ for 1-1.5h, solidified at 70-75℃ for 10-15min, and air dried at 50-55℃ for 2-2.5h, to obtain the modified down feather B.

[0013] In S4 of the modification method, the modified down feather B is immersed in the modified solution II with a bath ratio of 1kg:(20-25L), vacuumed to-0.05MPa to-0.06MPa, stirred at 30-50rpm for 25-35min, restored to normal pressure and stirred for 40-50min, taken out, drained until no continuous dripping, immersed in a water solution containing 1wt%-1.2wt% acetic acid with a bath ratio of 1kg:(15-20L), stirred at 30-50rpm for 10-15min, taken out, drained until no continuous dripping, cleaned 2-3 times with deionized water with a bath ratio of 1kg:(15-20L), centrifugal dewatered at 400-600rpm for 5-8min, and air dried at 65-70℃ until the water content is 8wt%-10wt%, to obtain the modified down feather C.

[0014] In S5 of the modification method, the post-equilibrium treatment is: placing the modified down C in an environment of 25-30 DEG C and 60-65% RH for 24-30 hours of equilibrium; using a down fluffiness instrument for 1-2 minutes of mechanical fluffing treatment to restore fluffiness, to obtain the warm and anti-migration down fiber material.

[0015] The mechanical fluffing treatment includes gentle, patting and stirring.

[0016] In S2 of the modification method, the molecular weight Mw of the polyethylene imine is 600.

[0017] In S3 of the modification method, the molecular weight Mw of the polyvinyl alcohol is 102600.

[0018] In S3 of the modification method, the concentration of the aqueous anionic aliphatic polyurethane resin dispersion is 27 wt%.

[0019] The modification method of the warm and anti-migration down fiber material has the beneficial effects including: I. Activation step (S1): alkyl polyglycoside as a mild surfactant, cleaning down can remove surface impurities without damaging the fiber structure; sodium bicarbonate and fatty alcohol polyoxyethylene ether synergistic effect, through the weak alkaline environment to open the protein scale structure on the surface of down fiber, so that more hydroxyl (-OH) and amino (-NH2) are exposed. This provides sufficient binding sites for the subsequent PDA-PEI coating anchoring, ensuring the uniformity of the bottom modification.

[0020] II. Bottom anchoring (S2): dopamine (PDA) is oxidized and self-polymerized in Tris-HCl buffer, and forms an interpenetrating network with polyethylene imine (PEI, Mw=600) through covalent bond and hydrogen bond. The PDA-PEI bottom layer uses low molecular weight PEI (Mw=600) to penetrate the fiber gap, and co-polymerizes with dopamine to form a nanoscale continuous coating, which not only protects the protein structure but also avoids serious weight gain. The coating not only enhances the fiber surface roughness through phenolic hydroxyl, but also provides active sites for subsequent cross-linking reaction due to the amino group of PEI, and at the same time, the hydrophobicity of PDA preliminarily reduces the moisture absorption rate of the fiber.

[0021] Three, dynamic crosslinking network (S3): PVA / WPU / Guar-HPTAC ratio optimization, PVA (3.0-3.5wt%) forms a hydrogen bond network to maintain flexibility in wet state; WPU (8-10wt%) provides elastic segment to resist compression deformation; Cationic groups of Guar-HPTAC (0.8-1.5wt%) are electrostatically adsorbed to the fiber to strengthen the crosslinking point. Polyvinyl alcohol (PVA), waterborne polyurethane (WPU) and guar gum hydroxypropyltrimethyl ammonium chloride (Guar-HPTAC) form borate ester bonds (B-O-C) under alkaline conditions through borax. The bond has dynamic reversibility: when the fiber is rubbed or extruded, part of the borate ester bond breaks to release stress, avoiding direct fiber breakage; after the external force disappears, the bond is reformed under the action of humidity and temperature, realizing self-repair. The flexible segment of WPU cooperates with the rigid segment of PVA, making the network both impact-resistant and shape-retaining, effectively inhibiting migration.

[0022] Four, hydrophobic aerogel loading (S4): the condensation reaction (Si-O-C covalent bond formation) between the amino group of the hydrophobic nano-silica aerogel and the phenolic hydroxyl group of the PDA coating, and the combination with the hydroxyl group of the PVA network, realizes multi-point anchoring. The superhydrophobicity of the aerogel further reduces the moisture absorption rate of the fiber, and its nanoporous structure locks still air, significantly improving the warmth retention.

[0023] Five, synergistic effect: the four-step treatment forms a three-layer structure of "bottom anchoring-intermediate buffering-surface hydrophobicity": the bottom anchoring phenolic hydroxyl-amino covalent bond with the fiber surface ensures that the modified layer does not fall off; the intermediate dynamic network PVA-WPU-Gu-Borax constructs a tangled dynamic bond energy consumption, and the intermediate network provides self-repairing and anti-migration ability; the surface aerogel fixes SiO2 aerogel-KH550 silane coupling agent to form Si-O-C covalent bond, and the surface enhances hydrophobicity and warmth retention. The three synergies make the initial loft retention rate very high (the loss of natural down loft is mainly due to the thickness of the coating, but it is offset by the network support), and in a humid and hot environment, due to the hydrophobicity and the air locking effect of the aerogel, the loft retention rate is high, the durability is good, and the performance degradation is slow.

[0024] Six, add BYK-349 surfactant to the modification liquid I, BYK-349 is a polyether modified siloxane surfactant, which reduces the surface tension of the modification liquid I, improves the compatibility of the components, especially the fusion of guar gum hydroxypropyltrimethyl ammonium chloride in the system, and improves the modification performance.

[0025] Seven, add Guar-HPTAC in the modified liquid I, Guar-HPTAC is a cationic guar gum derivative, combined with anionic WPU and PVA through electrostatic attraction, and physical entanglement is formed at the fiber intersection, providing the binding between components and interface, and improving the modification performance.

[0026] Eight, add appropriate amount of KH550 silane coupling agent in the modified liquid II, KH550 forms Si-O-C covalent bond through silicon hydroxyl and phenolic hydroxyl of PDA and hydroxyl of PVA, and can improve the compatibility of components, especially the surface modification of hydrophobic nano-silica aerogel powder, improve the adhesion amount of hydrophobic nano-silica aerogel powder, and then improve the modification effect.

[0027] Nine, add appropriate amount of BYK-111 dispersant in the modified liquid II, BYK-111 is a high molecular dispersant, which prevents the agglomeration of hydrophobic nano-silica aerogel through steric hindrance, and submits the uniform and dense adhesion of hydrophobic nano-silica aerogel.

[0028] Ten, add appropriate amount of cetyl alcohol phosphate in the modified liquid II to improve the compatibility; the cetyl alcohol phosphate is combined with the silicon hydroxyl of the aerogel through the phosphate group, and the long-chain alkyl is compatible with the hydrophobic segment of WPU, thereby enhancing the interface bonding force between the aerogel and the dynamic crosslinking network. DETAILED DESCRIPTION

[0029] The application will be further described below in combination with specific implementation examples, but the application is not limited to these examples.

[0030] Example 1:

[0031] A modification method of a warm and anti-migration down fiber material, the modification method comprising the following steps: S1, activation: according to the bath ratio 1kg:45, the goose down is cleaned with an aqueous solution containing 0.4wt% alkyl polyglycoside at 32℃ for 40min, and then washed with 32℃ deionized water for 3 times until no foam and clear water, centrifugal dewatering, and the water content is controlled to be 38%, to obtain clean down; according to the bath ratio 1kg:35L, the clean down is immersed in an aqueous solution containing 0.6wt% sodium bicarbonate and 1.2wt% fatty alcohol polyoxyethylene ether, and then stirred at 42℃ and 40rpm for 25min, and then washed with deionized water for 3 times, centrifugal dewatering, and the water content is controlled to be 47wt%, to obtain activated down. Purpose: moderately open the fiber surface scale / protein structure, expose more active groups (-OH, -NH2), and enhance the subsequent modification agent adsorption.

[0032] S2, bottom layer anchoring and protection: prepare a PDA-PEI solution by dissolving 2.2 g / L dopamine hydrochloride and 0.15 g / L polyethylenimine in a pH 8.2 Tris-HCl buffer; immerse the activated down in the PDA-PEI solution at a bath ratio of 1 kg:38 L, and treat it in an oxygen atmosphere (i.e., continuously supply 1 L / (min·kg down) of low-flow air) at 18°C with an oscillation amplitude of 8 cm and a frequency of 55 times / min for 4.5 h (low-temperature slow polymerization ensures uniform and dense PDA-PEI coating, avoiding agglomeration and clogging of pores); wash the down with deionized water for 3 times (to remove unreacted monomers and loose polymers); centrifuge and dewater at 500 rpm for 6 min; and air dry at 52°C for 1.5 h to obtain modified down A. Objective: To form a PDA-PEI nano-coating with strong adhesion on the fiber surface, provide a large number of active sites of phenolic hydroxyl groups / amino groups, and enhance the binding force of subsequent modifiers; meanwhile, PDA itself has certain hydrophobicity and anti-biodegradability, which improves the basic stability of the fiber.

[0033] S3, dynamic covalent cross-linking network construction: prepare an aqueous solution containing 3.2 wt% polyvinyl alcohol, 0.5 wt% borax, 9 wt% aqueous anionic aliphatic polyurethane resin dispersion (solid content 27 wt%), 0.2 wt% BYK-349 surfactant, and 1.2 wt% guar gum hydroxypropyltrimethylammonium chloride (Guar-HPTAC), and adjust the pH to 9.3 with sodium hydroxide to obtain a modification liquid I; immerse the modified down A in the modification liquid I at a bath ratio of 1 kg:28 L, vacuumize to-0.05 MPa, and stir at 40 rpm for 18 min (to ensure that the solution penetrates into the fiber bundle); restore to normal pressure and keep stirring for 35 min; take out, and drain the liquid without continuous dripping; place at 88% RH and 42°C for 1.5 h (borate ester bonds are initially formed in a humid environment), and solidify at 72°C for 12 min; and air dry at 53°C for 2.5 h to obtain modified down B. Objective: PVA, WPU, and Guar-HPTAC form a continuous film and physical entanglement on the fiber surface and fiber intersection points; borate ester bonds (B-O-C) provide dynamic and reversible cross-linking points, and endow the network with self-repairing ability. Under external force (including friction and extrusion), part of the borate ester bonds reversibly break to dissipate energy, reducing fiber breakage and migration; after the external force disappears, the bonds gradually recombine to restore the network structure, significantly improving the anti-migration durability. The combination of PVA, WPU, and Guar-HPTAC ensures that the film layer is flexible and breathable, without affecting the loftiness.

[0034] S4, hydrophobic aerogel loading: a water suspension containing 6 wt% hydrophobic nano-silica aerogel powder, 0.6 wt% KH550 silane coupling agent, 0.08% BYK-111 dispersant, 0.15 wt% polyether modified polydimethylsiloxane, 0.3 wt% cetyl alcohol phosphate, 22 wt% anhydrous ethanol, 5.5 wt% ammonia water (ammonia water concentration 26 wt%) was prepared to obtain modified liquid II; according to the bath ratio 1 kg:23 L, the modified down B was immersed in the modified liquid II, vacuumed to-0.05 MPa, 40 rpm stirring for 30 min, restored to normal pressure and kept stirring for 45 min; taken out, drained to no continuous dripping; according to the bath ratio 1 kg:18 L, immersed in 1.1 wt% acetic acid aqueous solution, 40 rpm stirring for 12 min, taken out, drained to no continuous dripping; according to the bath ratio 1 kg:18 L, washed with deionized water for 3 times, 500 rpm centrifugal dewatering for 6 min, 68℃ air drying to the water content of 9 wt%, to obtain modified down C. Purpose: ammonia catalyzes the condensation reaction between the phenolic hydroxyl group / amino group on the PDA coating and the residual silicon hydroxyl group on the aerogel surface and the hydroxyl group in the PVA, WPU and Guar-HPTAC network, forming covalent bond connection (Si-O-C, C-N), and strongly fixing the aerogel particles.

[0035] S5, the modified down C was placed in a 28℃, 63%RH environment for 26h; using the down fluffiness instrument for mechanical fluffing treatment including gentle, patting and stirring for 3min, to restore the fluffiness, to obtain the warm-keeping and anti-migration down fiber material.

[0036] Example 2:

[0037] A modification method of a warm-keeping and anti-migration down fiber material, the modification method comprising the following steps: S1, activation: according to the bath ratio 1 kg:40 L, the goose down was cleaned with a water solution containing 0.5 wt% alkyl polyglycoside at 30℃ for 50 min, washed with 30℃ deionized water for 4 times until no foam and clear water, centrifugal dewatering, controlling the water content of 40%, to obtain clean down; according to the bath ratio 1 kg:40 L, the clean down was immersed in a water solution containing 0.5 wt% sodium bicarbonate and 1.5 wt% fatty alcohol polyoxyethylene ether, stirring at 40℃, 50 rpm for 20 min, washed with deionized water for 3 times, centrifugal dewatering, controlling the water content of 45 wt%, to obtain activated down. Purpose: moderately open the fiber surface scale / protein structure, expose more active groups (-OH, -NH2), and enhance the subsequent adsorption of modifiers.

[0038] S2, bottom layer anchoring and protection: prepare a PDA-PEI solution by dissolving 2.5 g / L dopamine hydrochloride and 0.1 g / L polyethyleneimine in a pH 8.5 Tris-HCl buffer; immerse the activated down in the PDA-PEI solution at a bath ratio of 1 kg: 35 L, and treat it in an oxygen atmosphere (i.e., continuously supply 1.2 L / (min·kg down) of low-flow oxygen) at 15°C with an oscillation amplitude of 10 cm and a frequency of 50 times / min for 5 h (low-temperature slow polymerization ensures uniform and dense PDA-PEI coating, avoiding agglomeration and clogging of pores); wash with deionized water for 3 times (remove unreacted monomers and loose polymers); centrifuge for 5 min at 600 rpm; and dry at 55°C with air blowing for 1 h to obtain modified down A. Objective: form a PDA-PEI nano-coating with strong adhesion on the fiber surface, provide a large number of active sites of phenolic hydroxyl groups / amino groups, and enhance the binding force of subsequent modifiers; meanwhile, PDA itself has certain hydrophobicity and anti-biodegradability, which improves the basic stability of the fiber.

[0039] S3, dynamic covalent cross-linking network construction: prepare an aqueous solution containing 3.5 wt% polyvinyl alcohol, 0.4 wt% borax, 10 wt% aqueous anionic aliphatic polyurethane resin dispersion (solid content 27 wt%), 0.1 wt% BYK-349 surfactant, and 1.5 wt% guar gum hydroxypropyltrimethylammonium chloride (Guar-HPTAC), and adjust the pH to 9 with sodium hydroxide to obtain a modification liquid I; immerse the modified down A in the modification liquid I at a bath ratio of 1 kg: 30 L, vacuumize to -0.05 MPa, and stir at 50 rpm for 15 min (to ensure that the solution penetrates into the fiber bundle); restore to normal pressure and keep stirring for 40 min; take out, drain the liquid without continuous dripping, and stand at 85% RH and 45°C for 1 h (borate ester bonds are initially formed in a humid environment), and then solidify at 75°C for 10 min; and dry at 55°C with air blowing for 2 h to obtain modified down B. Objective: PVA, WPU, and Guar-HPTAC form a continuous film and physical entanglement on the fiber surface and fiber intersection points; borate ester bonds (B-O-C) provide dynamic reversible cross-linking points, endowing the network with self-repairing ability. Under external force (including friction and extrusion), part of the borate ester bonds reversibly break to dissipate energy, reducing fiber breakage and migration; after the external force disappears, the bonds gradually rebuild to restore the network structure, significantly improving the anti-migration durability. The combination of PVA, WPU, and Guar-HPTAC ensures that the film layer is flexible and breathable, without affecting the loftiness.

[0040] S4, hydrophobic aerogel loading: a water suspension containing 7wt% hydrophobic nano-silica aerogel powder, 0.5wt% KH550 silane coupling agent, 0.1% BYK-111 dispersant, 0.1wt% polyether modified polydimethylsiloxane, 0.5wt% cetyl alcohol phosphate, 20wt% anhydrous ethanol, 6wt% ammonia water (ammonia water concentration 25wt%) was prepared to obtain modified liquid II; according to the bath ratio 1kg:25L, the modified down B was immersed in the modified liquid II, vacuumed to-0.05MPa, 50rpm stirring for 25min, restored to normal pressure and kept stirring for 50min; taken out, drained to no continuous dripping; according to the bath ratio 1kg:15L, immersed in 1.2wt% acetic acid aqueous solution, 30rpm stirring for 15min, taken out, drained to no continuous dripping; according to the bath ratio 1kg:15L, washed with deionized water for 3 times, 400rpm centrifugal dewatering for 8min, 65℃ air drying to the moisture content of 10wt%, to obtain modified down C. Purpose: ammonia catalyzes the condensation reaction between the phenolic hydroxyl group / amino group on the PDA coating and the residual silicon hydroxyl group on the aerogel surface and the hydroxyl group in the PVA, WPU and Guar-HPTAC network, forming covalent bond connection (Si-O-C, C-N), and strongly fixing the aerogel particles.

[0041] S5, the modified down C was placed in a 25℃, 65%RH environment for 24h; using the down fluffiness instrument, mechanical fluffing treatment including gentle, patting and stirring was carried out for 4min to restore the fluffiness, to obtain the warm-keeping and anti-migration down fiber material.

[0042] Example 3:

[0043] A modification method of a warm-keeping and anti-migration down fiber material, the modification method comprising the following steps: S1, activation: according to the bath ratio 1kg:50L, the duck down was cleaned with a water solution containing 0.3wt% alkyl polyglycoside at 35℃ for 30min, washed with deionized water for 3 times until no foam and clear water, centrifugal dewatering, controlling the moisture content of 45%, to obtain clean down; according to the bath ratio 1kg:30L, the clean down was immersed in a water solution containing 0.8wt% sodium bicarbonate and 1.0wt% fatty alcohol polyoxyethylene ether, stirring at 45℃, 30rpm for 30min, washed with deionized water for 2 times, centrifugal dewatering, controlling the moisture content of 50wt%, to obtain activated down. Purpose: moderately open the fiber surface scale / protein structure, expose more active groups (-OH, -NH2), and enhance the subsequent adsorption of modifiers.

[0044] S2, bottom layer anchoring and protection: prepare a PDA-PEI solution by dissolving 2.0 g / L dopamine hydrochloride and 0.2 g / L polyethylenimine in a pH 8.0 Tris-HCl buffer; immerse the activated down in the PDA-PEI solution at a bath ratio of 1 kg:40 L, and treat it in an oxygen atmosphere (i.e., continuously supply 0.8 L / (min·kg down) of low-flow air) at 20°C with oscillation at an amplitude of 5 cm and a frequency of 60 times / min for 4 h (low-temperature slow polymerization ensures uniform and dense PDA-PEI coating, avoiding agglomeration and clogging of pores); wash the down with deionized water 4 times (to remove unreacted monomers and loose polymers); centrifuge and dewater at 400 rpm for 8 min; and dry at 50°C with air blowing for 1.5 h to obtain modified down A. Purpose: form a PDA-PEI nano-coating with strong adhesion on the fiber surface, provide a large number of active sites of phenolic hydroxyl groups / amino groups, and enhance the binding force of subsequent modifiers; meanwhile, PDA itself has certain hydrophobicity and anti-biodegradability, which improves the basic stability of the fiber.

[0045] S3, dynamic covalent cross-linking network construction: prepare a water solution containing 3.0 wt% polyvinyl alcohol, 0.6 wt% borax, 8 wt% aqueous anionic aliphatic polyurethane resin dispersion (solid content 27 wt%), 0.3 wt% BYK-349 surfactant, and 0.8 wt% guar gum hydroxypropyltrimethylammonium chloride (Guar-HPTAC), and adjust the pH to 9.5 with sodium hydroxide to obtain a modification liquid I; immerse the modified down A in the modification liquid I at a bath ratio of 1 kg:25 L, vacuumize to-0.06 MPa, and stir at 30 rpm for 20 min (to ensure that the solution penetrates into the fiber bundle); restore to normal pressure and keep stirring for 30 min; take out, and drain the liquid without continuous dripping; place at 90% RH and 40°C for 1.5 h (borate ester bonds are initially formed in a humid environment), and solidify at 70°C for 15 min; and dry at 50°C with air blowing for 2.5 h to obtain modified down B. Purpose: PVA, WPU, and Guar-HPTAC form a continuous film and physical entanglement on the fiber surface and fiber intersection points; borate ester bonds (B-O-C) provide dynamic and reversible cross-linking points, and endow the network with self-repairing ability. Under external force (including friction and extrusion), part of the borate ester bonds reversibly break to dissipate energy, reducing fiber breakage and migration; after the external force disappears, the bonds gradually rebuild to restore the network structure, significantly improving the anti-migration durability. The combination of PVA, WPU, and Guar-HPTAC ensures that the film layer is flexible and breathable, without affecting the loftiness.

[0046] S4, hydrophobic aerogel loading: a water suspension containing 5wt% hydrophobic nano-silica aerogel powder, 0.8wt% KH550 silane coupling agent, 0.05% BYK-111 dispersant, 0.2wt% polyether modified polydimethylsiloxane, 0.2wt% cetyl alcohol phosphate, 25wt% anhydrous ethanol, 5wt% ammonia water (ammonia water concentration 28wt%) was prepared to obtain modified liquid II; according to the bath ratio 1kg:20L, the modified down B was immersed in the modified liquid II, vacuumed to-0.06MPa, 30rpm stirring for 35min, restored to normal pressure and kept stirring for 40min; taken out, drained to no continuous dripping; according to the bath ratio 1kg:20L, immersed in 1wt% acetic acid aqueous solution, 50rpm stirring for 10min, taken out, drained to no continuous dripping; according to the bath ratio 1kg:20L, washed with deionized water for 2 times, 600rpm centrifugal dehydration for 5min, 70℃ air drying to 8wt% moisture content, to obtain modified down C. Purpose: ammonia catalytic PDA coating on the phenolic hydroxyl / amino and aerogel surface residual silanol and PVA, WPU, Guar-HPTAC network of hydroxyl condensation reaction, form covalent bond connection (Si-O-C, C-N), strong fixed aerogel particles.

[0047] S5, the modified down C was placed in 30℃, 60%RH environment, and equilibrated for 30h; using down fluffiness instrument, mechanical fluffing treatment including gentle, pat and stirring for 3min, to restore fluffiness, to obtain warm-keeping and anti-migration down fiber material.

[0048] The raw material sources involved in the above embodiments: the alkyl polyglycoside is from Guangzhou Jincheng Chemical Co., Ltd., model APG-0810. The fatty alcohol polyoxyethylene ether is from Shandong Moore Chemical Co., Ltd., model OP-10. The dopamine hydrochloride is from Sichuan Weiqi Biological Technology Co., Ltd., model WKQ-0002128. The polyethyleneimine has a molecular weight Mw=600 and is from Guangzhou Jiangshun Chemical Technology Co., Ltd. The polyvinyl alcohol has a molecular weight Mw=102600 and is from Shanghai Zhenjun Biological Technology Co., Ltd., model PVOH102K. The borax is from Guangzhou Jiaxin Technology Co., Ltd., purity 99.9%. The aqueous anionic aliphatic polyurethane resin dispersion (solid content 27 wt%) is from Evonik, model NeoRez R-610. The BYK-349 surfactant is distributed by Foshan Zhiqiao New Material Co., Ltd. The guar gum hydroxypropyltrimethyl ammonium chloride is from Shenzhen Xingkaiyue Biological Technology Co., Ltd. The hydrophobic nano-silica aerogel powder is from Langfang Laichang Energy-saving Technology Co., Ltd., item No. 03. The KH550 silane coupling agent is from Guangzhou Suixin Chemical Co., Ltd. The BYK-111 dispersant is distributed by Suzhou Huiwangcheng Chemical Co., Ltd. The polyether-modified polydimethylsiloxane is from Wuhan Huaxiang Kejebio Technology Co., Ltd., model SP-983. The cetyl alcohol phosphate is from Linyi Shangcheng Jiapu Industrial Raw Material E-commerce Operating Department, model AK-S16.

[0049] Comparative Example 1 The difference from Example 1 is that in S2, the amount of dopamine hydrochloride added is changed to 0.15 g / L, and the amount of polyethyleneimine added is changed to 2.2 g / L.

[0050] Comparative Example 2 The difference from Example 1 is that in S2, the polyethyleneimine is changed to have a molecular weight Mw=1800.

[0051] Comparative Example 3 The difference from Example 1 is that in S3, the aqueous anionic aliphatic polyurethane resin dispersion is not added in the modified liquid I.

[0052] Comparative Example 4 The difference from Example 1 is that in S3, the amount of aqueous anionic aliphatic polyurethane resin dispersion added in the modified liquid I is changed to 18 wt%.

[0053] Comparative Example 5 The difference from Example 1 is that in S3, the BYK-349 surfactant is not added in the modified liquid I.

[0054] Comparative Example 6 The difference from Example 1 is that in S3, the guar gum hydroxypropyltrimethyl ammonium chloride is not added in the modified liquid I. Comparative Example 7 The difference from Example 1 is that in S3, the amount of guar gum hydroxypropyltrimethyl ammonium chloride added in the modification liquid I is changed to 5wt%.

[0055] Comparative Example 8 The difference from Example 1 is that in S3, the pH of the modification liquid I is adjusted to 7.

[0056] Comparative Example 9 The difference from Example 1 is that in S3, the step of “curing at 72℃ for 12min” is omitted.

[0057] Comparative Example 10 The difference from Example 1 is that in S4, no KH550 silane coupling agent is added in the modification liquid II.

[0058] Comparative Example 11 The difference from Example 1 is that in S4, the KH550 silane coupling agent in the modification liquid II is replaced by KH171 silane coupling agent.

[0059] Comparative Example 12 The difference from Example 1 is that in S4, no BYK-111 dispersant is added in the modification liquid II.

[0060] Comparative Example 13 The difference from Example 1 is that in S4, the BYK-111 dispersant in the modification liquid II is replaced by BYK-349.

[0061] Comparative Example 14 The difference from Example 1 is that in S4, no polyether modified polydimethylsiloxane is added in the modification liquid II.

[0062] Comparative Example 15 The difference from Example 1 is that in S4, no cetyl alcohol phosphate is added in the modification liquid II.

[0063] The source of the replaced raw materials in the above comparative examples: polyethyleneimine molecular weight Mw=1800, from Beijing Naisi Biotechnology Co., Ltd., product code R016788. KH171 silane coupling agent is from Hubei Jianghao New Material Technology Co., Ltd.

[0064] The loft of the goose down raw material used in the above Example 1 is 740cm 3 / 28.4g.

[0065] The loft of the goose down raw material used in the above Example 2 is 750cm 3 / 28.4g.

[0066] The loft of the duck down raw material used in the above Example 3 is 780cm 3 / 28.4g.

[0067] The modified down of each of the above examples and comparative examples was subjected to performance detection as follows.

[0068] I. Initial bulkiness detection: Instrument: standard bulkiness instrument (diameter 28.4 cm cylinder + 68.5 g pressure plate), constant temperature and humidity chamber (20°C, 65% RH), electronic balance; Steps: 1. The sample was equilibrated in a standard environment (20°C, 65% RH) for 48 h; 2. 28.4 g of the sample was weighed; 3. Placed in the cylinder, naturally settled for 60 s; 4. Lightly placed the pressure plate, and the volume (cm 3 ) was read after 60 s; 5. Bulkiness = volume reading (cm 3 ), directly output cm 3 / 28.4 g.

[0069] II. Wet heat bulkiness retention rate: Instrument: constant temperature and humidity chamber (40°C, 95% RH), instrument used for initial bulkiness detection; Steps: 1. The sample after the initial bulkiness test was placed in a 40°C, 95% RH environment for 48 h; 2. After taking out, equilibrated in a standard environment (20°C, 65% RH) for 4 h; 3. The volume V1 after the wet heat treatment was tested according to the initial bulkiness method; 4. Retention rate (%) = (V1 / initial bulkiness) x 100%.

[0070] III. Anti-migration detection: Instrument: Martindale abrasion tester, 20D nylon fabric (pore size ≈ 70 μm, simulating real fabric); Steps: 1. Preparation of sandwich sample: 20D nylon cloth on the upper and lower layers, 100 g / m 2 of modified down filled in the middle, size 10 cm x 10 cm; 2. Fixed on the Martindale instrument, 9 kPa pressure was applied (simulating clothing stress); 3. Two-way friction at 100 rpm for 500 times; 4. After taking out, the mass of the drilled down Δm (μg) was weighed; 5. Anti-migration = Δm (μg).

[0071] IV. Warmth retention detection: Instrument: hot plate instrument; sample mold (30 x 30 x 2.5 cm); Step: 1. Fill density 120 g / m 2 Uniformly fill the mold, standard test fabric package; 2. Hot plate temperature 35℃, cold plate temperature -20℃; record heat flux q (W / m 2 ) after 40 min of stabilization; 3. Thermal resistance R = ΔT / q (m 2 ·K / W), converted to CLO value.

[0072] Five, durability test: Standard basis: AATCC 135-2018 (household washing) Instrument: standard washing machine (including rotating cage), oven (50℃); fluffiness, anti-migration and warmth detection instrument; Step: 1. Prepare anti-migration samples of the same specification (20D nylon sandwich); 2. Washing procedure: 40℃ water temperature, AATCC standard 1993 type detergent 4g / L, bath ratio 1:30, normal mode washing for 45 min; 3. Drying: tumble drying at 40℃ to constant weight, and equilibrating for 24h under standard environment (20℃, 65%RH); 4. Test fluffiness, down amount, CLO value after 20 cycles; 5. Calculate retention rate: Fluffiness retention rate (%) = (fluffiness after 20 times / initial) x 100%; Warmth retention rate (%) = (CLO value after 20 times / initial) x 100%; Anti-migration deterioration rate (%) = (down amount after 20 times / initial) x 100%.

[0073] Table 1 Performance test results (interval value of 3 parallel samples)

[0074] From the above results, it can be seen that the modified down of examples 1 to 3 has good performance advantages: (1) Activation step (S1): alkyl polyglycoside as a mild surfactant, cleaning down removes surface impurities without damaging the fiber structure; sodium bicarbonate and fatty alcohol polyoxyethylene ether synergistically act to open the protein scale structure on the surface of down fibers through a weak alkaline environment, exposing more hydroxyl groups (-OH) and amino groups (-NH2). This provides sufficient binding sites for the anchoring of the subsequent PDA-PEI coating, ensuring the uniformity of the bottom modification.

[0075] (2) Bottom anchoring (S2): Dopamine (PDA) is oxidized and self-polymerized in Tris-HCl buffer solution, and forms an interpenetrating network with polyethyleneimine (PEI, Mw=600) through covalent bonds and hydrogen bonds. The PDA-PEI bottom layer uses low molecular weight PEI (Mw=600) to penetrate the fiber gap and copolymerize with dopamine to form a nanoscale continuous coating that not only protects the protein structure but also avoids severe weight gain. This coating not only enhances the surface roughness of the fiber through phenolic hydroxyl groups, but also provides active sites for subsequent cross-linking reactions due to the amino groups of PEI, while the hydrophobicity of PDA initially reduces the moisture absorption rate of the fiber.

[0076] (3) Dynamic cross-linking network (S3): PVA / WPU / Guar-HPTAC ratio optimization, PVA (3.0-3.5wt%) forms a hydrogen bond network to maintain flexibility in a wet state; WPU (8-10wt%) provides elastic segments to resist compression deformation; Cationic groups of Guar-HPTAC (0.8-1.5wt%) are electrostatically adsorbed to the fiber to strengthen the crosslinking point. Polyvinyl alcohol (PVA), waterborne polyurethane (WPU), and guar gum hydroxypropyltrimethylammonium chloride (Guar-HPTAC) form borate ester bonds (B-O-C) under alkaline conditions. This bond is dynamically reversible: when the fiber is rubbed or squeezed, some of the borate ester bonds break to release stress, preventing the fiber from breaking directly; after the external force disappears, the bond is reformed under the action of humidity and temperature, achieving self-repair. The flexible segments of WPU and the rigid segments of PVA work together to make the network both impact-resistant and shape-preserving, effectively inhibiting migration.

[0077] (4) Hydrophobic aerogel loading (S4): Hydrophobic nano-silica aerogel condensation reaction (Si-O-C covalent bond) occurs between the amino groups of KH550 silane coupling agent and the phenolic hydroxyl groups of the PDA coating, while also combining with the hydroxyl groups of the PVA network, achieving multi-point anchoring. The superhydrophobicity of the aerogel further reduces the moisture absorption rate of the fiber, and its nanoporous structure locks still air, significantly improving warmth retention.

[0078] (5) Synergistic effect: The four-step process forms a three-layer structure of "bottom anchoring-intermediate buffer-surface hydrophobicity": the bottom anchoring phenolic hydroxyl-amino covalent bond to the fiber surface ensures that the modified layer does not fall off; the intermediate dynamic network PVA-WPU-Gu-Borax builds a tangled dynamic bond energy consumption, and the intermediate network provides self-repairing and anti-migration capabilities; the surface aerogel SiO2 aerogel-KH550 silane coupling agent forms a Si-O-C covalent bond, enhancing the hydrophobicity and warmth retention of the surface. The three work together to maintain a high initial loft retention rate (the loss of natural down loft is mainly due to coating thickness, but this is offset by the network support), and in a humid and hot environment, due to the hydrophobicity and aerogel air-locking effect, the loft retention rate is high, the durability is good, and the performance degradation is slow.

[0079] Comparative Example 1 (the ratio of dopamine to polyethyleneimine is reversed in S2) has a defective coating structure: when dopamine (0.15 g / L) is much lower than PEI (2.2 g / L), the oxidative polymerization of PDA is insufficient, and the low dopamine concentration leads to low polymerization degree, and the coating formed is mainly PEI, and the excessive PEI leads to excessive free amino groups, which not only causes the brittleness of the cross-linked coating, but also competes with the borate ester bond in the subsequent modification solution I, causing the bonding force of the dynamic cross-linked network to decrease. The coating is of poor quality and cannot provide sufficient support, and the fibers are prone to lodging; the insufficient PDA leads to poor hydrophobicity, and the fibers aggregate after absorbing moisture, and the volume shrinkage is more obvious; the adhesion between the coating and the fibers is weak, and the coating is easily detached during friction, and the fiber exposure increases; during the washing process, the PEI-based coating has a high water solubility, and after 20 washes, the coating retention rate is low, and the performance retention rate decreases.

[0080] Comparative Example 2 (the molecular weight of PEI is changed to 1800 in S2) is affected by steric hindrance: The long-chain structure of high molecular weight PEI (Mw=1800) hinders the oxidative polymerization of PDA, leading to a decrease in the interpenetration of PDA and PEI in the coating, and the coating only covers the surface layer of the fiber, and the anchoring depth is insufficient; stress concentration is caused by uneven macromolecular coating, and the coating is uneven. Local coating is too thick, causing fiber gaps to be blocked, and the bulkiness is lower than that of the embodiment; the uneven area is prone to moisture absorption, causing local fibers to aggregate and the retention rate to decrease; uneven anchoring leads to uneven adhesion of the subsequent coating, and the drilling rate increases; the long chain of PEI is easily broken by the shear force of the water flow during washing, and the coating performance retention rate is lower after washing.

[0081] Comparative Example 3 (no water-based polyurethane resin is contained in S3) has a defective network structure: after the absence of WPU, the dynamic cross-linked network is mainly composed of PVA and Guar-HPTAC, and due to the lack of flexible segments, the network glass transition temperature increases from -10°C in the embodiment to 20°C, and the brittleness increases. The binding force at the fiber intersection point decreases, and it cannot effectively inhibit the fiber sliding. The network is easily brittle during friction, the fiber constraint is weakened, and the drilling rate is higher; the network lacks elasticity, and after absorbing moisture, it cannot buffer the fiber expansion stress, and the structure collapses more obviously, and the retention rate decreases; during the washing process, the network gradually disintegrates due to brittleness, and the fiber loss after washing is higher than that of the embodiment, and the bulkiness and warmth retention rate decrease.

[0082] Comparative Example 4 (the addition amount of WPU is too high at 18 wt% in S3) has an excessive coating accumulation: The excess of WPU causes the viscosity of modified liquid I to increase, the pores to be blocked, and a thick coating to be formed on the surface of the fibers. The coating is formed due to the over-strong film-forming property of WPU, which increases the adhesion points between the fibers and seriously hinders the fluffy expansion. The thick coating increases the rigidity of the fiber bundle, and the volume after natural settlement is lower than that of the embodiment; the hydrophilic groups (ester groups) of WPU increase with the increase of the content, and the moisture absorption rate is higher than that of the embodiment, and the fiber gap is further reduced after the coating swells; the thick coating is prone to breakage due to stress concentration when rubbed, and the amount of broken down fibers is higher than that of the embodiment; the resin swells during washing, the bonding force between the thick coating and the fibers decreases due to the high internal stress, and the performance attenuation after washing is large.

[0083] The interfacial tension and compatibility problem of Comparative Example 5 (S3 does not contain BYK-349 surfactant): BYK-349 is a polyether-modified siloxane surfactant, which can reduce the surface tension of modified liquid I and improve the compatibility of the components, especially the fusion of Guar-HPTAC in the system. After being missing, the modified liquid I has poor compatibility, poor film-forming quality, uneven stress, local performance short board, local defects, and affects various performances. During washing, the durability is poor.

[0084] The entanglement force deficiency of Comparative Example 6 (S3 does not contain Guar-HPTAC): Guar-HPTAC is a cationic guar derivative, which combines with anionic WPU and PVA through electrostatic attraction to form physical entanglement at the intersection of fibers. After being missing, the fibers are only connected by borate ester bonds, the integrity of the network decreases, and the structural stability decreases. The sliding resistance between fibers decreases, and the amount of down fibers increases after 500 times of friction; the network is prone to loosen after absorbing moisture due to the lack of entanglement, the fiber lodging is more obvious, and the retention rate decreases; the fiber aggregation degree is higher than that of the embodiment after washing, and the retention rate of fluffiness decreases.

[0085] The over-crosslinking problem of Comparative Example 7 (S3 has an excessive amount of 5wt% of Guar-HPTAC): The excess of Guar-HPTAC causes the viscosity of modified liquid I to increase, and forms excessive entanglement with PVA and WPU, which leads to excessive adhesion points between the fiber bundles and forms a thick and uneven coating on the surface of the fibers, which hinders the fluffy expansion. Excessive adhesion limits the fiber stretching, and the fluffiness is lower than that of the embodiment. Guar-HPTAC is a hydrophilic polysaccharide, and the excess causes the overall moisture absorption rate to be higher than that of the embodiment, and the uneven stress is prone to breakage under stress, and the short fibers after breaking are more prone to drilling; the network with excessive entanglement is brittle due to high rigidity during washing, and the durability decreases.

[0086] Comparative Example 8 (pH of modification solution in S3 is adjusted to 7): Borate ester bond formation is insufficient: Boric acid (H3BO3) mainly exists in molecular form under neutral conditions (pH = 7), and the efficiency of forming borate ester bonds with the hydroxyl groups of PVA is much lower than that under alkaline conditions. The cross-linking density of the dynamic cross-linking network is reduced, and the self-repairing ability is basically lost. The network function is invalid, the network cannot dissipate stress through bond rupture, and the fiber is directly broken by friction, resulting in a higher drilling and carding amount than the embodiment; the network is loose, the fiber is easily aggregated due to moisture absorption, and the retention rate is reduced; the durability is reduced.

[0087] Comparative Example 9 (omit the solidification step at 72°C in S3): Insufficient cross-linking degree: The solidification step (70-75°C) promotes the condensation reaction of borate ester bonds, increasing the cross-linking degree. After omission, the structure is loose. The network support is insufficient, the fiber is prone to lodging, and the loftiness is lower than the embodiment; the loose network is more prone to collapse in a humid and hot environment, and the retention rate is reduced; the constraint between fibers is weak, and the fiber is prone to sliding when rubbed, resulting in an increased drilling and carding amount; the unsolidified network is easily washed away by water flow, and the network retention rate is low after washing, and the performance decays significantly.

[0088] Comparative Example 10 (no KH550 silane coupling agent in S4): Covalent bond loss and poor compatibility: KH550 forms Si-O-C covalent bonds with the phenolic hydroxyl groups of PDA and the hydroxyl groups of PVA through silicon hydroxyl groups, and can improve the compatibility of components, especially the surface modification of hydrophobic nano-silica aerogel powder, and increase the adhesion amount of hydrophobic nano-silica aerogel powder. After being lost, the aerogel is only adsorbed on the fiber surface through van der Waals force, and the bonding force is reduced, and the function of the aerogel is greatly reduced. The aerogel is prone to agglomeration, the air locking ability is reduced, and the CLO value is lower than the embodiment; the fiber in the aerogel shedding area is prone to moisture absorption, resulting in a decrease in the overall retention rate; the agglomeration of the aerogel leads to an increase in the local friction coefficient, but the fiber in the shedding area is exposed, resulting in an increased drilling and carding amount; the aerogel is lost in large quantities during washing due to weak bonding force, and the hydrophobic and warm-keeping performance decays severely.

[0089] Comparative Example 11 (KH550 is replaced by KH171 in S4): Difference in reaction activity: KH171 contains vinyl groups (-CH=CH2), and the surface modification of the aerogel is poor, the number of covalent bonds between the aerogel and the fiber is reduced, and the bonding force is reduced; which further affects various performances, but is better than Comparative Example 10.

[0090] Comparative Example 12 (no BYK-111 dispersant in S4): Aerogel agglomeration: BYK-111 is a high molecular dispersant that prevents hydrophobic nano-silica aerogel from agglomerating through steric hindrance. After being lost, the aerogel agglomerates due to van der Waals force and is unevenly distributed. Large-diameter agglomerates block the gaps between fibers, resulting in a lower loftiness than the embodiment; the porosity of the agglomerates is reduced, the air locking ability is reduced, and the CLO value is reduced; the agglomerates are prone to fall off when rubbed, resulting in an increased broken drilling and carding amount; the bonding force between the agglomerates and the fiber is weak, the shedding rate increases after washing, and the performance decays rapidly.

[0091] Comparative Example 13 (BYK-111 replaced by BYK-349 in S4) dispersion efficiency difference: BYK-349 mainly reduces surface tension, and the dispersion ability is lower than BYK-111 (the anchoring group of BYK-111 has stronger binding force with the silicon hydroxyl group on the surface of aerogel), and part of the aerogel is still agglomerated. The performance is better than that of Comparative Example 12, but lower than that of Example 1.

[0092] Comparative Example 14 (no polyether-modified polydimethylsiloxane in S4) insufficient hydrophobicity: polyether-modified polydimethylsiloxane enhances hydrophobicity by reducing the surface energy of aerogel. After being missing, the moisture absorption rate is higher than that of the example. After absorbing moisture, the aerogel expands in volume, squeezing the gap between the fibers, resulting in more obvious decrease in loftiness, and lower retention rate after washing; the surface adhesion of the fibers increases after absorbing moisture, but the binding force between the aerogel and the fibers decreases due to moisture absorption, and part of the fibers fall off with the aerogel during friction, resulting in increased drilling of the fibers; repeated moisture absorption-drying cycles gradually damage the structure of the aerogel, resulting in low retention rate of hydrophobicity after washing, and accelerated degradation of warmth retention and anti-migration.

[0093] Comparative Example 15 (no cetyl alcohol phosphate in S4) compatibility defect: cetyl alcohol phosphate is an amphoteric surfactant, which binds to the silicon hydroxyl group of the aerogel through the phosphate group, and is compatible with the hydrophobic segment of WPU through the long-chain alkyl group, thereby enhancing the interfacial binding force between the aerogel and the dynamic cross-linked network. After being missing, the compatibility between the aerogel and the network decreases, and the interfacial binding is poor. The coverage of the aerogel on the fiber surface is low, and the moisture absorption in the exposed area causes the fibers to aggregate, resulting in lower retention rate than the example; the interface gap makes the aerogel easy to fall off from the network, and the fibers in the falling-off area lose protection, resulting in increased drilling of the fibers; water flow easily invades from the interface gap during washing, accelerating the separation of the aerogel and the network, resulting in lower retention rate of the aerogel and obvious performance degradation after washing than the example.

Claims

1. A method of modifying a thermal, migration resistant, down fiber material, characterized in that, The modification method comprises the following steps: S1, activation: immersing the washed down feather into an aqueous solution containing sodium bicarbonate and fatty alcohol polyoxyethylene ether, washing, dehydrating, and obtaining activated down feather; S2, bottom anchoring and protection: preparing a pH 8.0-8.5 Tris-HCl buffer solution containing 2.0 g / L-2.5 g / L dopamine hydrochloride and 0.1 g / L-0.2 g / L polyethyleneimine to obtain a PDA-PEI solution; immersing the activated down feather into the PDA-PEI solution, oscillating treatment, washing, dehydrating, and air drying to obtain modified down feather A; S3, dynamic covalent cross-linking network construction: preparing an aqueous solution containing 3.0 wt%-3.5 wt% polyvinyl alcohol, 0.4 wt%-0.6 wt% borax, 8 wt%-10 wt% aqueous anionic aliphatic polyurethane resin dispersion, 0.1 wt%-0.3 wt% BYK-349 surfactant, and 0.8 wt%-1.5 wt% guar gum hydroxypropyltrimethylammonium chloride, adjusting to pH 9-9.5 to obtain a modification liquid I; immersing the modified down feather A into the modification liquid I, vacuumizing to-0.05 MPa--0.06 MPa, stirring at 30 rpm-50 rpm for 15 min-20 min, restoring to normal pressure and keeping stirring for 30 min-40 min, taking out, draining, standing, solidifying, and air drying to obtain modified down feather B; S4, hydrophobic aerogel loading: preparing a water suspension containing 5 wt%-7 wt% hydrophobic nano-silica aerogel powder, 0.5 wt%-0.8 wt% KH550 silane coupling agent, 0.05%-0.1% BYK-111 dispersant, 0.1 wt%-0.2 wt% polyether-modified polydimethylsiloxane, 0.2 wt%-0.5 wt% cetyl alcohol phosphate, 20 wt%-25 wt% anhydrous ethanol, and 5 wt%-6 wt% ammonia water to obtain a modification liquid II; immersing the modified down feather B into the modification liquid II, vacuumizing to-0.05 MPa--0.06 MPa, stirring at 30 rpm-50 rpm for 25 min-35 min, restoring to normal pressure and keeping stirring for 40 min-50 min, taking out, draining, immersing into an aqueous solution containing 1 wt%-1.2 wt% acetic acid, stirring, taking out, and draining; washing with deionized water for 2-3 times, centrifugal dehydrating, and air drying to obtain modified down feather C; S5, carrying out performance balancing post-treatment on the modified down feather C to obtain a warm-keeping and anti-migration down feather material.

2. The method of modifying a thermal, migration resistant down fiber material according to claim 1, wherein, In S1, the activation is as follows: immersing the washed down feather into an aqueous solution containing 0.5 wt%-0.8 wt% sodium bicarbonate and 1.0 wt%-1.5 wt% fatty alcohol polyoxyethylene ether at a bath ratio of 1 kg:(30 L-40 L), stirring at 40℃-45℃ and 30 rpm-50 rpm for 20 min-30 min, washing with deionized water for 2-3 times, centrifugal dehydrating, and controlling the water content to be 45 wt%-50 wt% to obtain the activated down feather.

3. A method of modifying a thermal, anti-migratory down fiber material according to claim 1 or 2, characterized in that, The cleaning method of the washed down feather includes: using a water solution containing 0.3wt%-0.5wt% alkyl polysaccharide to clean the down feather at 30-35℃ for 30-50min with a bath ratio of 1kg:(40-50L), cleaning 3-4 times with deionized water at 30-35℃ until no foam and clear water, centrifugal dewatering, and controlling the water content to be less than or equal to 45% to obtain the washed down feather.

4. The method of modifying a thermal, migration resistant down fiber material according to claim 3, wherein, The down feather is goose feather or duck feather.

5. The method of modifying a thermal, migration resistant down fiber material according to claim 1, wherein, In S2, the activated down feather is immersed in the PDA-PEI solution with a bath ratio of 1kg:(35-40L), oscillation treatment for 4-5h under oxygen atmosphere at 15-20℃, cleaned 3-4 times with deionized water, centrifugal dewatering for 5-8min at 400-600rpm, and air drying at 50-55℃ for 1-1.5h to obtain the modified down feather A.

6. The method of modifying a thermal, migration resistant, down fiber material according to claim 1, wherein, In S3, the modified down feather A is immersed in the modified liquid I with a bath ratio of 1kg:(25-30L), vacuumed to-0.05 to-0.06MPa, stirred at 30-50rpm for 15-20min, restored to normal pressure and stirred for 30-40min, taken out, drained until no continuous dripping, placed at 85-90%RH and 40-45℃ for 1-1.5h, solidified at 70-75℃ for 10-15min, and air dried at 50-55℃ for 2-2.5h to obtain the modified down feather B.

7. The method of modifying a thermal, migration resistant, down fiber material according to claim 1, wherein, In S4, the modified down feather B is immersed in the modified liquid II with a bath ratio of 1kg:(20-25L), vacuumed to-0.05 to-0.06MPa, stirred at 30-50rpm for 25-35min, restored to normal pressure and stirred for 40-50min, taken out, drained until no continuous dripping, immersed in 1wt%-1.2wt% acetic acid solution with a bath ratio of 1kg:(15-20L), stirred at 30-50rpm for 10-15min, taken out, drained until no continuous dripping, cleaned 2-3 times with deionized water with a bath ratio of 1kg:(15-20L), centrifugal dewatering at 400-600rpm for 5-8min, and air dried at 65-70℃ until the water content is 8-10wt% to obtain the modified down feather C.

8. The method of modifying a thermal, migration resistant, down fiber material according to claim 1, wherein, In S5, the post-equilibrium treatment is to place the modified down feather C in an environment of 25-30℃ and 60-65%RH for 24-30h, and mechanically fluffy treatment for 1-2min using a down feather fluffiness instrument to obtain the warm-keeping and anti-migration down feather material.

9. The method of modifying a thermal, migration resistant down fiber material according to claim 8, wherein, The mechanical fluffy treatment includes gentle, patting and stirring.

10. The method of modifying a thermal, migration resistant, down fiber material according to claim 1, wherein, In S2, the molecular weight of the polyethylene imine is Mw=600; in S3, the molecular weight of the polyvinyl alcohol is Mw=102600; and in S3, the concentration of the water-based anionic aliphatic polyurethane resin dispersion is 27wt%. In S2, the molecular weight of the polyethylene imine is Mw=600; in S3, the molecular weight of the polyvinyl alcohol is Mw=102600; and in S3, the concentration of the water-based anionic aliphatic polyurethane resin dispersion is 27wt%.

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