Salt-resistant and detergent-resistant alginate fiber for clothing and preparation method of alginate fiber

Abstract

The invention discloses a salt-resistant and detergent-resistant alginate fiber for clothing and a preparation method thereof, and belongs to the technical field of functional textile materials. The fiber is prepared from the following raw materials: sodium alginate, an organic silicon-phosphatide copolymer, a zwitterionic polymer, calcium chloride, polyethylene glycol octylphenol ether and deionized water. Wherein the organic silicon-phosphatide copolymer is prepared by reacting methacryloyloxypropyltrimethoxysilane, methacrylic acid-2-hydroxyethyl phosphate and the like in methylbenzene under the protection of nitrogen, performing reduced pressure distillation, performing ethanol precipitation and drying; the zwitterionic polymer is prepared by polymerizing acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and the like in deionized water under the protection of nitrogen, chopping, precipitating with acetone and drying. The preparation method comprises the following steps: adding water into the sodium alginate, stirring, and adding the copolymer, the zwitterionic polymer and the polyethylene glycol octylphenol ether to obtain a modified spinning solution; and spinning until a calcium chloride solution is formed, soaking in water, and drying in vacuum. The fiber can be used in garments.

Description

Technical Field

[0001] The present invention relates to the technical field of functional textile materials, and in particular to salt-resistant and detergent-resistant seaweed fiber for clothing and a preparation method thereof. Background Art

[0002] As a natural polymer material, seaweed fiber has been widely used in medical dressings, tissue engineering and other fields due to its good biocompatibility, degradability and unique "egg-box" cross-linking structure. However, its application in the field of clothing has long been limited by its insufficient salt resistance and detergent resistance. As daily consumer goods, clothing is frequently exposed to complex environments such as sweat and detergents. Ordinary seaweed fibers are prone to excessive swelling of the molecular chains due to ion penetration in high-salt solutions, and their mechanical properties are significantly reduced. Under the action of detergents, surfactant molecules will destroy their "egg-box" cross-linking structure, reducing the durability of the fiber and limiting its promotion in outdoor clothing, sportswear and other scenarios.

[0003] Traditional seaweed fiber modification technologies mostly use a single cross-linking agent to strengthen or simply graft functional groups to improve performance, but it is difficult to meet the multiple needs in complex environments. For example, the traditional process using calcium ions as a single cross-linking agent can improve the initial strength through the "egg-box" structure, but its ability to inhibit the long-term penetration of salt ions is limited. In a high-salt environment, the fiber will still increase its swelling rate due to ion exchange; and the method of grafting modification with acrylic monomers can introduce hydrophilic or hydrophobic groups, but the grafting process can easily destroy the original molecular chain regularity of sodium alginate, and the modified functional groups are easily hydrolyzed or detached due to the acid-base environment in the detergent, resulting in insufficient durability. In addition, the problem of organic reagent residues introduced by some modification technologies may also affect the biocompatibility and wearing safety of the fiber, further restricting its application expansion in the clothing field.

[0004] With the growing demand for functional clothing among consumers, the development of a seaweed fiber that is both salt-resistant and detergent-resistant and environmentally friendly has become an urgent need in the industry. In the existing technology, there is no solution that can improve the seaweed fiber's resistance to salt ion penetration and surfactant damage without destroying its original structure through the synergistic effect of bifunctional modified compounds. Some studies have attempted to improve performance through composite modifiers, but there are problems such as poor compatibility and uneven dispersion of modifiers, which lead to an imbalance between the mechanical properties and functional stability of the fiber. Therefore, exploring the preparation process of new modified compounds and their synergistic mechanism in seaweed fibers is of great significance for promoting the application of seaweed fibers in the clothing field. Summary of the Invention

[0005] The purpose of the present invention is to provide a salt-resistant and detergent-resistant seaweed fiber for clothing and a preparation method thereof, which solves the technical problems of poor salt resistance and insufficient detergent resistance of existing seaweed fibers in clothing applications.

[0006] The present invention achieves the above-mentioned purpose through the following technical solutions:

[0007] A salt-resistant and detergent-resistant seaweed fiber comprises the following raw materials in parts by weight:

[0008] Sodium alginate: 50-150 parts by weight;

[0009] Organosilicon-phosphite copolymer: 10-30 parts by weight;

[0010] Zwitterionic polymer: 5-20 parts by weight;

[0011] Calcium chloride: 1-5 parts by weight;

[0012] Polyethylene glycol octylphenyl ether: 0.5-2 parts by weight;

[0013] Deionized water: 790-980 parts by weight;

[0014] The preparation method of the organosilicon-phosphite copolymer includes: A1, adding methacryloyloxypropyltrimethoxysilane, methacrylic acid-2-hydroxyethyl phosphate, and azobisisobutyronitrile to a three-necked flask filled with toluene, passing nitrogen to deoxygenate, and heating to 74-76°C for reaction; A2, after the reaction is completed, performing reduced pressure distillation, precipitating the product with anhydrous ethanol, filtering, and vacuum drying.

[0015] In this invention, the formation mechanism of the organosilicon-phosphoester copolymer stems from the free radical copolymerization of two functional monomers. One monomer contains a siloxane group and a polymerizable double bond, while the other carries a hydroxyl group, a phosphate group, and a polymerizable double bond. In a toluene solution under inert gas, the initiator decomposes to produce free radicals that attack the double bonds of both monomers, initiating a chain propagation reaction. Due to the different reactivities of the two monomers, the copolymerization process gradually forms an alternating or randomly linked molecular chain structure: the siloxane groups tend to aggregate on one side of the chain segment, forming a hydrophobic organosilicon region; the phosphate groups and hydroxyl groups are distributed on the other side, forming a hydrophilic polar region. In the later stages of the reaction, the solvent is removed by vacuum distillation, and the polymer molecules are precipitated with anhydrous ethanol, ultimately yielding a copolymer with both hydrophobic segments and hydrophilic phosphoester groups. Within the product's molecular chain, the siloxane bonds provide excellent flexibility and weather resistance, while the phosphate groups retain active sites for metal ion coordination, laying the foundation for subsequent interaction with sodium alginate.

[0016] According to the preferred embodiment of the present application, in step A1, the oxygen removal time under nitrogen is 30-40 min; the reaction time at 74-76℃ is 6-8 h.

[0017] According to the preferred embodiment of the present application, in step A2, the temperature for vacuum drying is 40-42℃, and the time is 12-14 h.

[0018] According to the preferred embodiment of the present application, the preparation method of the zwitterionic polymer comprises: B1, dissolving acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and N-(3-aminopropyl) dimethylallyl ammonium chloride in deionized water, removing oxygen under nitrogen, and then adding ammonium persulfate and sodium bisulfite successively to initiate polymerization and heat to 60-64℃ to react; B2, after the reaction is completed, the gelatinous product is cut into pieces, precipitated with acetone, filtered and vacuum dried.

[0019] In the present application, the construction of the zwitterionic polymer is based on the free radical copolymerization process of three functional monomers. One of the monomers is a neutral amide compound, which provides the backbone structure of the molecular chain; another monomer carries a sulfonic acid group, which endows the molecular chain with anionic characteristics; the third monomer contains a polymerizable amino group and a quaternary ammonium salt group, which introduces a cationic active site. In deionized water protected by inert gas, the free radicals generated by the decomposition of the initiator attack the double bonds or amino active sites of the three monomers, initiating chain growth reaction. Due to the strong electron-withdrawing effect of the sulfonic acid group and the strong electron-donating effect of the quaternary ammonium salt group, the three monomers tend to alternate in the polymerization process, forming regions in the molecular chain that contain both anions (sulfonate groups) and cations (quaternary ammonium groups). In the later stage of the reaction, by cutting, acetone precipitation and vacuum drying, a polymer with zwitterionic characteristics is obtained. In the molecular chain of the product, the sulfonic acid group can dissociate into a negative charge in water, and the quaternary ammonium group remains a positive charge, forming an internal salt structure; this zwitterionic structure endows the polymer with good water solubility and electrostatic neutralization ability for anions and cations, providing a functional basis for subsequent neutralization of the detergent surfactant.

[0020] According to the preferred embodiment of the present application, in step B1, the reaction time at 60-64℃ is 4-6 h.

[0021] According to the preferred embodiment of the present application, in step B2, the temperature for vacuum drying is 50-52℃, and the time for vacuum drying is 12-14 h.

[0022] The present application also provides a preparation method of the salt-tolerant and detergent-tolerant seaweed fiber, comprising the following steps:

[0023] S1, sodium alginate is added to deionized water and stirred at 60-64℃ to obtain a solution; the organosilicon-phosphorus ester copolymer, the zwitterionic polymer and the polyethylene glycol octylphenyl ether are sequentially added to the sodium alginate solution and continuously stirred until completely dissolved to obtain a modified spinning solution;

[0024] S2, the modified spinning solution is extruded through a spinneret into a calcium chloride solution to form fibers; the fibers are soaked in deionized water and then vacuum dried at 60-64℃.

[0025] In the present application, the formation of the seaweed fiber is the result of the synergistic effect of the sodium alginate molecular chain and various modifiers. As the basic fiber-forming material, the molecular chain of sodium alginate is formed by the connection of β-D-mannuronic acid and α-L-guluronic acid through 1,4-glycosidic bond, and is rich in hydroxyl and carboxyl groups. When sodium alginate is dissolved in water, the molecular chain forms a viscous spinning solution through hydrogen bonding and electrostatic interaction. As a crosslinking agent, the calcium ions of calcium chloride can coordinate with the carboxyl groups on the molecular chain of sodium alginate to form a primary crosslinking network with an "egg box" structure, giving the spinning solution an initial gel property. The addition of the organosilicon-phosphorus ester copolymer further strengthens this process: the phosphate groups in the molecular chain of the copolymer coordinate with the carboxyl groups of sodium alginate and calcium ions to form secondary crosslinking points in the gaps of the "egg box" structure, increasing the crosslinking density; at the same time, the hydrophobic organosilicon segments of the copolymer tend to aggregate on the surface of the fiber to form a hydrophobic barrier, reducing the penetration of salt ions into the interior of the fiber. The zwitterionic polymer interacts with the surfactant molecules in the detergent through electrostatic interaction: the anionic groups in the molecular chain of the zwitterionic polymer can neutralize the cationic surfactants (such as quaternary ammonium salts) in the detergent, and the cationic groups can neutralize the anionic surfactants (such as alkyl sulfates), thereby reducing the stripping effect of the surfactants on the "egg box" crosslinked structure. In addition, the addition of the emulsifier improves the dispersibility of the organosilicon-phosphorus ester copolymer (hydrophobic segment) and the zwitterionic polymer (polar group) in the sodium alginate solution, avoids defects in spinning caused by phase separation, and ensures the uniformity of the fiber cross section. Finally, through spinning, calcium chloride solution crosslinking and water washing and drying, seaweed fibers with stable "egg box" structure, resistance to salt ion penetration and resistance to detergent damage are formed.

[0026] According to the preferred embodiment of the present application, in step S1, the stirring time at 60-64℃ is 2-4h; the continuous stirring time is 1-2h.

[0027] According to the preferred embodiment of the present application, in step S2, the soaking time in deionized water is 24-30h; the vacuum drying time at 60-64℃ is 2-4h.

[0028] The present application also provides the use of the salt-resistant and detergent-resistant seaweed fiber or the salt-resistant and detergent-resistant seaweed fiber prepared by the preparation method in garments.

[0029] The beneficial effects of the present application are:

[0030] The seaweed fiber of the present application realizes systematic improvement in salt resistance, detergent resistance and overall performance through the synergistic design of bifunctional modification compounds and process optimization, providing a new material solution with functionality and durability for the clothing field. In view of the core problem of insufficient salt resistance of traditional seaweed fiber, the present application introduces an organic silicon-phosphorus ester copolymer to construct a double protection mechanism. The hydrophobic silicon segment of the copolymer can form a dense interface barrier on the fiber surface, effectively blocking the penetration path of salt ions to the material interior; at the same time, the phosphorus ester groups contained therein can chemically interact with the polar groups of the sodium alginate molecular chain and external calcium ions, forming a stable crosslinked network, enhancing the compactness and ion erosion resistance of the internal structure of the fiber. This synergistic effect of "physical barrier-chemical crosslinking" fundamentally inhibits the destruction of salt ions to the fiber structure, significantly improving the stability of the material in a high salt environment.

[0031] In terms of detergent resistance performance optimization, the introduction of zwitterionic polymer plays a key role. The molecular chain of the polymer has both positive and negative charge groups, which can interact with surfactant molecules in detergents through electrostatic interaction, reducing their ability to strip the "egg box" crosslinked structure of seaweed fiber; at the same time, the hydrophilic nature of the zwitterion can adjust the swelling balance of the fiber in different environments, avoiding excessive swelling or shrinkage caused by detergent penetration. This dual inhibition of surfactant damage effectively maintains the integrity of the fiber structure, allowing it to maintain good mechanical properties and service life under complex washing conditions.

[0032] From the overall performance synergy, the combination of components in the formula further enhances the functional performance of the material. Calcium chloride, as a traditional crosslinking agent, forms a basic crosslinked structure with the polar groups of sodium alginate, providing a stable anchoring site for the modifier; the addition of emulsifier improves the dispersibility of the hydrophobic modifier and the polar polymer in the spinning solution, avoiding defects caused by phase separation, ensuring the uniformity of the fiber cross-section and the consistency of the mechanical properties. This synergistic effect of multiple components allows the fiber to maintain the biocompatibility and biodegradability of natural seaweed fiber while considering softness and durability, better meeting the dual demands of functionality and comfort in the clothing field, providing innovative material support for the development of functional clothing. DETAILED DESCRIPTION

[0033] The following detailed description is only used to further illustrate the present application and cannot be understood as limiting the scope of protection of the present application. Those skilled in the art can make some non-essential improvements and adjustments to the present application based on the above application content.

[0034] The information of domestic suppliers of relevant equipment and materials is as follows:

[0035] The sodium alginate was purchased from Qingdao Mingyue Seaweed Group Co., Ltd.

[0036] The methacryloyloxypropyltrimethoxysilane was purchased from Nanjing Shuguang Silane Chemical Co., Ltd.

[0037] The methacrylate-2-hydroxyethyl phosphate was purchased from Jiangsu Hehai Nanotechnology Co., Ltd.

[0038] The azobisisobutyronitrile was purchased from Jinan Shengfang Chemical Co., Ltd.

[0039] The toluene was purchased from the Zhenhai Refining and Chemical Company of China Petrochemical Corporation.

[0040] The three-necked flask was purchased from Gongyi Yuhua Instrument Co., Ltd.

[0041] The nitrogen was purchased from Yingde Gas Group Co., Ltd.

[0042] The anhydrous ethanol was purchased from Jiangsu Hengli Petrochemical Co., Ltd.

[0043] The calcium chloride was purchased from Hebei Jinniu Chemical Co., Ltd.

[0044] The polyethylene glycol octylphenyl ether was purchased from Liaoning Aoke Chemical Co., Ltd.

[0045] The acrylamide was purchased from Shandong Baomo Biochemical Co., Ltd.

[0046] The 2-acrylamido-2-methylpropanesulfonic acid was purchased from Henan Qingshuiyuan Technology Co., Ltd.

[0047] The N-(3-aminopropyl)dimethylallylammonium chloride was purchased from Jiangsu Feixiang Chemical Co., Ltd.

[0048] The ammonium persulfate was purchased from Shandong Hongda Chemical Co., Ltd.

[0049] The sodium bisulfite was purchased from Hebei Jiheng Pharmaceutical Co., Ltd.

[0050] The acetone was purchased from Jiangsu Hengrui Medicine Co., Ltd.

[0051] Example 1

[0052] Preparation of silicone-phosphorus ester copolymer: Methyl methacryloyloxypropyl trimethoxysilane 120 g, methyl methacrylate-2-hydroxyethyl phosphate 80 g, azobis isobutyronitrile 2 g were sequentially added into a three-necked flask containing toluene 300 g, a reflux condenser and a thermometer were installed, and nitrogen was introduced to remove air in the flask. After 30 min, the nitrogen valve was closed. A magnetic stirrer was turned on and stirred at 300 rpm, and the flask was placed in an oil bath to slowly heat. When the temperature reached 75 °C, it was kept constant for 6 h. During the reaction, the temperature and stirring state were recorded every 30 min to ensure the stability of the reaction. After the reaction was completed, the oil bath was turned off, and the reaction solution was transferred to a rotary evaporator after the flask was cooled to room temperature. The temperature was set to 60 °C, and the vacuum degree was -0.09 MPa for vacuum distillation until the toluene was basically removed (about 40 min). The residue after distillation was poured into a beaker, 200 mL of anhydrous ethanol was added and stirred uniformly. After standing for 30 min, it was filtered with qualitative filter paper. The filter cake was collected and placed in a vacuum drying oven, set to 40 °C, vacuum degree -0.08 MPa, and dried for 12 h to obtain white powder silicone-phosphorus ester copolymer.

[0053] Preparation of zwitterionic polymer: Acrylamide 60 g, 2-acrylamido-2-methylpropane sulfonic acid 30 g, N-(3-aminopropyl)dimethylallyl ammonium chloride 10 g were sequentially added into a glass beaker containing deionized water 566.7 g, and stirred at 200 rpm with a handheld stirrer for 15 min until completely dissolved to prepare an aqueous solution with a total solid content of 15%. The beaker was transferred to a constant temperature water bath, set to 60 °C and kept constant, and nitrogen was introduced to remove oxygen in the solution. After 20 min, the nitrogen valve was closed. Ammonium persulfate 0.1 g and sodium bisulfite 0.1 g were sequentially weighed and dissolved in a small amount of deionized water, then added dropwise to the beaker. At the same time, the stirring speed was increased to 500 rpm. After the initiator was completely dissolved, stirring was continued for 5 min. Then the temperature of the water bath was increased to 62 °C and kept constant for 4 h. After the reaction was completed, the water bath was turned off, and the gelatinous product was picked out with a glass rod after the beaker was cooled to room temperature. It was put into a tissue crusher and crushed at 1000 rpm for 2 min. The crushed pieces were poured into a beaker, 200 mL of acetone was added and stirred uniformly. After standing for 30 min, it was filtered with quantitative filter paper. The filter cake was collected and placed in a vacuum drying oven, set to 50 °C, vacuum degree -0.08 MPa, and dried for 12 h to obtain a light yellow granular zwitterionic polymer.

[0054] Preparation of salt-tolerant and detergent-tolerant seaweed fiber: 100 g of sodium alginate was weighed and added to 856 g of deionized water in a stainless steel reaction kettle with a stirring paddle. The stirrer was turned on and stirred at 300 rpm while the reaction kettle was heated to 62°C. The temperature was kept constant and stirring was continued for 2 h until the sodium alginate was completely dissolved, resulting in a transparent viscous spinning dope. 20 g of silicone-phosphorus ester copolymer, 10 g of zwitterionic polymer, and 1 g of polyethylene glycol octylphenyl ether were added to the spinning dope in sequence, and stirring was continued at 300 rpm for 1 h until all the additives were completely dissolved, resulting in a uniform modified spinning dope. The modified spinning dope was extruded through a spinning machine equipped with a 0.08 mm diameter spinneret at a speed of 0.5 m / min into a calcium chloride solution (1% by mass solution prepared by dissolving 3 g of calcium chloride in 300 g of water). The distance between the spinneret and the liquid surface was kept at 10 cm during the extrusion process to form a continuous fiber bundle. The fiber bundle was immersed in deionized water for 24 h (the deionized water was replaced every 8 h to completely remove the residual calcium chloride and unreacted modifiers). After soaking, the fiber was taken out and placed in a vacuum drying oven, set at a temperature of 62°C and a vacuum degree of -0.08 MPa, and dried for 2 h to obtain a light brown salt-tolerant and detergent-tolerant seaweed fiber.

[0055] Example 2

[0056] The specific implementation is the same as Example 1, except that the preparation of the silicone-phosphorus ester copolymer: methylacryloxypropyl trimethoxysilane 130 g, methylacrylic acid-2-hydroxyethyl phosphate 70 g, azobis isobutyronitrile 2 g are added to a three-necked flask containing toluene 300 g, deoxygenated by nitrogen for 35 min, and then heated to 76℃ for 7 h. After the reaction is completed, toluene is removed by distillation under reduced pressure, and the product is precipitated with anhydrous ethanol, filtered and vacuum dried to obtain the silicone-phosphorus ester copolymer. Preparation of the zwitterionic polymer: acrylamide 55 g, 2-acrylamido-2-methylpropane sulfonic acid 35 g, N-(3-aminopropyl) dimethylallyl ammonium chloride 10 g are dissolved in deionized water 555.6 g, deoxygenated by nitrogen for 25 min, and then ammonium persulfate 0.1 g and sodium bisulfite 0.1 g are added to initiate polymerization, and the temperature is raised to 64℃ for 5 h. After the reaction is completed, the gelatinous product is cut into small pieces, precipitated with acetone, filtered and vacuum dried to obtain the zwitterionic polymer. Preparation of salt-resistant and detergent-resistant seaweed fibers: sodium alginate 120 g is added to deionized water 826.7 g, and stirred at 64℃ for 3 h to obtain a solution; silicone-phosphorus ester copolymer 25 g, zwitterionic polymer 15 g, and polyethylene glycol octylphenyl ether 1.5 g are sequentially added to the sodium alginate solution, and stirring is continued for 1.5 h until complete dissolution to obtain a modified spinning solution; the modified spinning solution is extruded through a spinneret into a calcium chloride solution (calcium chloride 4 g dissolved in 400 g water) to form fibers; the fibers are soaked in deionized water for 27 h (water is changed every 8 h), and then vacuum dried at 64℃ for 3 h to obtain seaweed fibers.

[0057] Example 3

[0058] The specific implementation is the same as example 1, except that the preparation of the silicone-phosphorus ester copolymer: methyl methacryloyloxypropyl trimethoxysilane 110 g, methacrylic acid-2-hydroxyethyl phosphate 90 g, azobis isobutyronitrile 2 g are added to a three-necked flask containing toluene 300 g, deoxygenated by nitrogen for 30 min, and then heated to 74°C for 8 h; after the reaction is completed, toluene is removed by distillation under reduced pressure, and the product is precipitated with anhydrous ethanol, filtered and vacuum dried to obtain the silicone-phosphorus ester copolymer. Preparation of the zwitterionic polymer: acrylamide 65 g, 2-acrylamido-2-methylpropanesulfonic acid 25 g, N-(3-aminopropyl)dimethylallyl ammonium chloride 10 g are dissolved in deionized water 571.4 g, deoxygenated by nitrogen for 20 min, and then ammonium persulfate 0.1 g and sodium bisulfite 0.1 g are added in sequence to initiate polymerization, and the temperature is raised to 60°C for 6 h; after the reaction is completed, the gelatinous product is cut into small pieces, precipitated with acetone, filtered and vacuum dried to obtain the zwitterionic polymer. Preparation of the salt-resistant and detergent-resistant seaweed fiber: sodium alginate 150 g is added to deionized water 806.7 g, stirred at 60°C for 4 h to obtain a solution; the silicone-phosphorus ester copolymer 15 g, the zwitterionic polymer 5 g, and the polyethylene glycol octylphenyl ether 0.5 g are sequentially added to the sodium alginate solution, and the stirring is continued for 2 h until complete dissolution to obtain a modified spinning solution; the modified spinning solution is extruded through a spinneret into a calcium chloride solution (calcium chloride 5 g dissolved in 500 g of water) to form a fiber; the fiber is soaked in deionized water for 30 h (water is changed every 8 h), and then vacuum dried at 60°C for 4 h to obtain the seaweed fiber.

[0059] Comparative Example 1

[0060] The specific implementation is the same as example 1, except that the preparation of the salt-resistant and detergent-resistant seaweed fiber: sodium alginate 100 g is added to deionized water 856.7 g, stirred at 62°C for 2 h to obtain a solution; the zwitterionic polymer 10 g and the polyethylene glycol octylphenyl ether 1 g are sequentially added to the sodium alginate solution, and the stirring is continued for 1 h until complete dissolution to obtain a modified spinning solution (without adding the silicone-phosphorus ester copolymer); the modified spinning solution is extruded through a spinneret into a calcium chloride solution (calcium chloride 3 g dissolved in 300 g of water) to form a fiber; the fiber is soaked in deionized water for 24 h (water is changed every 8 h), and then vacuum dried at 62°C for 2 h to obtain the seaweed fiber.

[0061] Comparative Example 2

[0062] The specific implementation method is the same as that of Example 1, except that, for the preparation of salt-resistant and detergent-resistant seaweed fiber, 100 g of sodium alginate was added to 856.7 g of deionized water and stirred at 62° C. for 2 h to obtain a solution; 20 g of organosilicon-phosphite copolymer and 1 g of polyethylene glycol octylphenyl ether were sequentially added to the sodium alginate solution and stirred for 1 h until completely dissolved to obtain a modified spinning solution (without adding a zwitterionic polymer); the modified spinning solution was extruded through a spinneret into a calcium chloride solution (3 g of calcium chloride dissolved in 300 g of water) to form fibers; the fibers were soaked in deionized water for 24 h (the water was changed every 8 h), and then vacuum-dried at 62° C. for 2 h to obtain the seaweed fiber.

[0063] Comparative Example 3

[0064] The specific implementation method is the same as that of Example 1, except that, for the preparation of salt-resistant and detergent-resistant seaweed fiber, 100 g of sodium alginate was added to 886.7 g of deionized water and stirred at 62° C. for 2 hours to obtain a solution; 1 g of polyethylene glycol octylphenyl ether was added to the sodium alginate solution and stirred for 1 hour until completely dissolved to obtain a modified spinning solution (without adding an organosilicon-phosphite copolymer and a zwitterionic polymer); the modified spinning solution was extruded through a spinneret into a calcium chloride solution (3 g of calcium chloride dissolved in 300 g of water) to form fibers; the fibers were soaked in deionized water for 24 hours (the water was changed every 8 hours), and then vacuum-dried at 62° C. for 2 hours to obtain the seaweed fiber.

[0065] Performance Testing

[0066] The salt-resistant and detergent-resistant seaweed fibers prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to performance tests according to the following methods:

[0067] Before testing salt and detergent resistance, all seaweed fiber samples were equilibrated in a standard temperature and humidity environment (25°C, 65% relative humidity) for 24 hours to ensure consistent testing conditions. For breaking strength and elongation testing, referring to GB / T 1447-2005, Test Methods for Tensile Properties of Fibers, a universal materials testing machine (accuracy ±1%) was used. Fibers were cut into specimens 200 mm long and 10 mm wide. These specimens were clamped between the chucks (20 mm gap) and tested at a tensile rate of 10 mm / min. The maximum load (N) and corresponding elongation (mm) at break were recorded. The breaking strength (cN / dtex, 1 cN / dtex = 0.001 N / mm × 9000 mm / tex) and elongation (%, elongation / initial length × 100%) were calculated. Each sample group was tested five times, and the average value was taken. Salt resistance test: Fiber samples were completely immersed in a 3.5% (mass fraction) sodium chloride solution at 25°C for 72 hours. After removal, the samples were rinsed twice with deionized water (5 minutes each time) and dried in a 60°C vacuum drying oven to constant weight. The swelling ratio was calculated as: swelling ratio = [(wet mass after immersion - initial dry mass) / initial dry mass] × 100%; the mass retention ratio was calculated as: mass retention = [mass after drying / initial dry mass] × 100%. Detergent resistance test: In accordance with GB / T 8629-2001, "Technical Requirements for Household Washing Machines for Textiles," a standard detergent solution (0.5% concentration, 40°C) was used in a vertical washing machine (5kg capacity). A standard wash cycle (15 minutes per wash, 50 rpm, 3 rinses, 800 rpm spin) was performed. After washing, the fiber samples were removed, rinsed twice with deionized water, and dried in a vacuum oven at 60°C to constant weight. The fiber's breaking strength after washing was tested, and the strength retention rate was calculated: Strength retention rate = [breaking strength after washing / initial breaking strength] × 100%. The fiber's surface morphology was also observed using a scanning electron microscope (SEM, accelerating voltage 5kV, magnification 500x) to assess the extent of structural damage. Comprehensive performance evaluation: The fiber's durability in complex environments was comprehensively assessed by combining breaking strength, elongation at break, swelling ratio, and strength retention rate after washing.

[0068] Performance test results:

[0069] Table 1: Performance test results of various embodiments and comparative examples

[0070]

[0071] As can be seen from Table 1, Examples 1-3, through comparative analysis with Comparative Examples 1-3, show that the present invention effectively solves the technical problems of poor salt resistance and insufficient detergent resistance of traditional seaweed fiber in clothing applications through the synergistic effect of the dual-modified compounds.

[0072] In terms of salt resistance, traditional seaweed fibers are prone to excessive swelling and reduced mass retention due to the combination of salt ions with hydroxyl and carboxyl groups on the molecular chain. The added silicone-phosphorus ester copolymer in Examples 1-3 forms a dense barrier through the hydrophobic silicone segment, reducing the penetration of salt ions into the fiber interior; the phosphorus ester groups contained therein form additional crosslinking points with sodium alginate carboxyl and calcium ions, enhancing the density of the "egg box" structure, thereby significantly reducing the swelling rate (Example 1 swelling rate 12.3±0.5%, far lower than 25.1±1.0% of Comparative Example 3) and increasing the mass retention rate (Example 1 mass retention rate 92.1±1.0%, higher than 82.4±1.5% of Comparative Example 3).

[0073] In terms of detergent resistance, the traditional seaweed fibers are prone to mechanical property degradation due to the destruction of the "egg box" structure by surfactants in detergents. The zwitterionic polymer added in Examples 1-3 neutralizes the electrostatic interaction of surfactants through the positive and negative charge groups on the molecular chain, reducing the stripping of the "egg box" structure; at the same time, its hydrophilic characteristics balance the fiber swelling degree, avoiding excessive swelling or shrinkage. Experimental data show that the breaking strength retention rate (86.2-87.5%) and breaking elongation retention rate (87.8-89.2%) of Examples 1-3 after washing are significantly higher than those of Comparative Example 3 (58.7±3.5% and 61.3±3.0% respectively), and SEM observation shows that the fiber structure of Examples is dense and has no obvious damage, while the "egg box" structure of Comparative Example 3 is severely damaged.

[0074] In summary, Examples 1-3 simultaneously improve the salt resistance and detergent resistance of the fibers through the synergistic effect of silicone-phosphorus ester copolymer (blocking salt ions, enhancing crosslinking) and zwitterionic polymer (neutralizing surfactants, balancing swelling), solving the problems of structural damage and insufficient durability of traditional seaweed fibers in clothing applications due to environmental factors, and providing technical support for their promotion in the clothing field.

[0075] The above-described examples only express several embodiments of the present application, and the description is more specific and detailed, but it should not be understood as limiting the scope of the present patent. It should be noted that for ordinary skilled persons in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the scope of protection of the present application.

Claims

1. A salt-resistant and detergent-resistant seaweed fiber, characterized in that: The invention comprises the following raw materials in parts by weight: Sodium alginate: 50-150 parts by weight; Organosilicon-phosphite copolymer: 10-30 parts by weight; Zwitterionic polymer: 5-20 parts by weight; Calcium chloride: 1-5 parts by weight; Polyethylene glycol octylphenyl ether: 0.5-2 parts by weight; Deionized water: 790-980 parts by weight; The preparation method of the organosilicon-phosphite copolymer includes: A1, adding methacryloyloxypropyltrimethoxysilane, methacrylic acid-2-hydroxyethyl phosphate, and azobisisobutyronitrile to a three-necked flask filled with toluene, passing nitrogen to deoxygenate, and heating to 74-76°C for reaction; A2, after the reaction is completed, performing reduced pressure distillation, precipitating the product with anhydrous ethanol, filtering, and vacuum drying.

2. The salt-resistant and detergent-resistant seaweed fiber according to claim 1, characterized in that: In step A1, the nitrogen deoxygenation time is 30-40 minutes; the temperature is raised to 74-76° C. and the reaction time is 6-8 hours.

3. The salt-resistant and detergent-resistant seaweed fiber according to claim 1, characterized in that: In step A2, the vacuum drying temperature is 40-42° C. and the time is 12-14 h.

4. The salt-resistant and detergent-resistant seaweed fiber according to claim 1, characterized in that: The preparation method of the zwitterionic polymer comprises the following steps: B1, dissolving acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, and N-(3-aminopropyl)dimethylallylammonium chloride in deionized water, passing nitrogen gas to remove oxygen, sequentially adding ammonium persulfate and sodium bisulfite to initiate polymerization, and heating to 60-64° C. for reaction; B2, after the reaction, chopping the colloidal product, precipitating it with acetone, filtering it, and vacuum drying it.

5. The salt-resistant and detergent-resistant seaweed fiber according to claim 4, characterized in that: In step B1, the temperature is raised to 60-64° C. and the reaction time is 4-6 h.

6. The salt-resistant and detergent-resistant seaweed fiber according to claim 4, characterized in that: In step B2, the vacuum drying temperature is 50-52° C., and the vacuum drying time is 12-14 h.

7. A method for preparing salt-resistant and detergent-resistant seaweed fiber according to any one of claims 1 to 6, characterized in that the steps include: S1. Add sodium alginate to deionized water and stir at 60-64° C. to obtain a solution; Adding organosilicon-phosphite copolymer, zwitterionic polymer and polyethylene glycol octylphenyl ether to the sodium alginate solution in sequence, and continuing to stir until completely dissolved to obtain a modified spinning solution; S2. Extruding the modified spinning solution into a calcium chloride solution through a spinneret to form fibers; soaking the fibers in deionized water, and then vacuum drying at 60-64° C.

8. The preparation method according to claim 7, characterized in that In step S1, the stirring time at 60-64° C. is 2-4 h; the stirring time is continued for 1-2 h.

9. The preparation method according to claim 7, characterized in that In step S2, the immersion time in deionized water is 24-30 hours; and the vacuum drying time at 60-64° C. is 2-4 hours.

10. Use of the salt-resistant and detergent-resistant seaweed fiber according to any one of claims 1 to 6 or the salt-resistant and detergent-resistant seaweed fiber prepared by the preparation method according to any one of claims 7 to 9, characterized in that: Application of the salt-resistant and detergent-resistant seaweed fiber in clothing.

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