A salt- and detergent-resistant seaweed fiber for clothing and its preparation method
By synergistically modifying the seaweed fiber with organosilicon-phospholipid copolymer and zwitterionic polymer, the problem of insufficient salt resistance and detergent resistance in clothing applications was solved, and the structural stability and durability of the fiber in complex environments were improved.
Patent Information
- Application Number
- CN202511285534.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-10
- Publication Date
- 2026-01-06
- Estimated Expiration
- 2045-09-10
AI Technical Summary
Existing seaweed fibers have poor salt resistance and insufficient detergent resistance in clothing applications, making it difficult to maintain mechanical properties and structural stability in complex environments.
Seaweed fibers were bifunctionally modified using organosilicon-phospholipid copolymers and zwitterionic polymers. The hydrophobic organosilicon segments formed a barrier to block the penetration of salt ions, while the zwitterionic polymers neutralized the electrostatic effects of detergent surfactants, thereby enhancing the stability of the fiber's cross-linked structure.
It significantly improves the stability and detergent resistance of seaweed fiber in high-salt environments, maintains the integrity of the fiber structure and its service life, and meets the diverse needs of the apparel industry.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of functional textile materials technology, specifically to a salt-resistant and detergent-resistant seaweed fiber for clothing and its preparation method. Background Technology
[0002] Seaweed fiber, as a natural polymer material, has been widely used in medical dressings, tissue engineering, and other fields due to its excellent biocompatibility, biodegradability, and unique "egg-box" cross-linking structure. However, its application in the clothing industry has long been limited by insufficient salt resistance and detergent resistance. As everyday consumer goods, clothing is frequently exposed to complex environments such as sweat and detergents. Ordinary seaweed fiber is prone to excessive swelling of molecular chains due to ion penetration in high-salt solutions, resulting in a significant decrease in mechanical properties. Under the action of detergents, surfactant molecules can destroy its "egg-box" cross-linking structure, reducing the fiber's durability and limiting its promotion in outdoor clothing, sportswear, and other scenarios.
[0003] Traditional seaweed fiber modification technologies often employ single cross-linking agents or simple grafting of functional groups to enhance performance, but these methods struggle to meet the diverse demands of complex environments. For instance, the traditional process using calcium ions as a single cross-linking agent, while improving initial strength through an "egg-box" structure, has limited long-term resistance to salt ion penetration; in high-salt environments, the fiber's swelling rate still increases due to ion exchange. While acrylic monomer grafting modification can introduce hydrophilic or hydrophobic groups, the grafting process easily disrupts the original molecular chain regularity of sodium alginate, and the modified functional groups are prone to hydrolysis or detachment in the acidic or alkaline environments of detergents, leading to insufficient durability. Furthermore, the residual organic reagents introduced by some modification technologies may affect the fiber's biocompatibility and wearing safety, further limiting its application in the apparel industry.
[0004] With the increasing consumer demand for functional clothing, developing seaweed fiber that is both salt-resistant and detergent-resistant, as well as environmentally friendly, has become an urgent industry need. Currently, there is no solution that can simultaneously improve the resistance to salt ion penetration and surfactant damage of seaweed fiber without damaging its original structure through the synergistic effect of bifunctional modifying compounds. Some studies have attempted to improve performance through composite modifiers, but these suffer from poor compatibility and uneven dispersion, leading to an imbalance between the fiber's mechanical properties and functional stability. Therefore, exploring the preparation process of novel modifying compounds and their synergistic mechanism in seaweed fiber is of great significance for promoting the application of seaweed fiber in the clothing industry. Summary of the Invention
[0005] The purpose of this invention is to provide a salt-resistant and detergent-resistant seaweed fiber for clothing and its preparation method, 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 objectives through the following technical solutions:
[0007] A salt- and detergent-resistant seaweed fiber, comprising the following raw materials in parts by weight:
[0008] Sodium alginate: 50-150 parts by weight;
[0009] Organosilicon-phospholipid 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-phospholipid copolymer includes: A1, adding methacryloyloxypropyltrimethoxysilane, 2-hydroxyethyl methacrylate, and azobisisobutyronitrile to a three-necked flask containing toluene, purging with nitrogen to remove oxygen, and then heating to 74-76℃ for reaction; A2, after the reaction is completed, distilling under reduced pressure, precipitating the product with anhydrous ethanol, filtering, and vacuum drying.
[0015] In this invention, the formation mechanism of the organosilicon-phospholipid copolymer originates from the free radical copolymerization reaction of two functional monomers. One monomer contains a siloxane group and a polymerizable double bond, while the other monomer carries a hydroxyl group, a phosphate group, and a polymerizable double bond. In a toluene solution under inert gas protection, the initiator decomposes to generate free radicals, which attack the double bonds of the two monomers, initiating a chain growth reaction. Due to the difference in reactivity between the two monomers, an alternating or randomly linked molecular chain structure gradually forms during the copolymerization process: the siloxane group tends to aggregate on one side of the chain segment, forming a hydrophobic organosilicon region; the phosphate group and hydroxyl group are distributed on the other side, forming a hydrophilic polar region. In the later stage of the reaction, the solvent is removed by vacuum distillation, and anhydrous ethanol precipitates the polymer molecules, ultimately yielding a copolymer that simultaneously possesses hydrophobic segments and hydrophilic phosphate groups. In the molecular chain of this product, the siloxane bond provides good flexibility and weather resistance, while the phosphate group retains active sites for coordination with metal ions, laying the foundation for subsequent interaction with sodium alginate.
[0016] According to a preferred embodiment of the present invention, in step A1, the nitrogen deoxygenation time is 30-40 min; the reaction time is 6-8 h after heating to 74-76℃.
[0017] According to a preferred embodiment of the present invention, in step A2, the vacuum drying temperature is 40-42°C and the time is 12-14 hours.
[0018] According to a preferred embodiment of the present invention, the preparation method of the zwitterionic polymer includes: B1, dissolving acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, and N-(3-aminopropyl)dimethylallylammonium chloride in deionized water, removing oxygen by purging with nitrogen, and then sequentially adding ammonium persulfate and sodium bisulfite to initiate polymerization, and heating to 60-64°C for reaction; B2, after the reaction is completed, chopping the gelatinous product, precipitating it with acetone, filtering, and vacuum drying.
[0019] In this invention, the zwitterionic polymer is constructed based on a free radical copolymerization process of three functional monomers. One monomer is a neutral amide compound, providing the skeletal structure of the molecular chain; another monomer carries a sulfonic acid group, endowing the molecular chain with anionic properties; and the third monomer contains polymerizable amino and quaternary ammonium salt groups, introducing cationic active sites. In deionized water under inert gas protection, free radicals generated by the decomposition of the initiator attack the double bonds or amino active sites of the three monomers, initiating a chain propagation 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 during polymerization, forming regions in the molecular chain that simultaneously contain anions (sulfonic acid groups) and cations (quaternary ammonium groups). In the later stages of the reaction, the polymer with zwitterionic characteristics is obtained by chopping, precipitating with acetone, and vacuum drying. In the molecular chain of this product, the sulfonic acid group can dissociate into a negative charge in water, while the quaternary ammonium group stably maintains 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 detergent surfactants.
[0020] According to a preferred embodiment of the present invention, in step B1, the reaction time is 4-6 hours after heating to 60-64°C.
[0021] According to a preferred embodiment of the present invention, in step B2, the vacuum drying temperature is 50-52°C and the vacuum drying time is 12-14 hours.
[0022] This invention also provides a method for preparing the salt-resistant and detergent-resistant seaweed fiber described above, comprising the following steps:
[0023] S1. Add sodium alginate to deionized water and stir at 60-64℃ to obtain a solution; add organosilicon-phospholipid copolymer, zwitterionic polymer and polyethylene glycol octylphenyl ether to the sodium alginate solution in sequence and continue stirring until completely dissolved to obtain modified spinning solution.
[0024] S2. The modified spinning solution is extruded into a calcium chloride solution through a spinneret to form fibers; the fibers are soaked in deionized water and then vacuum dried at 60-64℃.
[0025] In this invention, the formation of seaweed fibers is the result of the synergistic effect of sodium alginate molecular chains and various modifiers. Sodium alginate, as the basic fiber-forming material, has molecular chains composed of β-D-mannuronic acid and α-L-guluronic acid linked by 1,4-glycosidic bonds, rich in hydroxyl and carboxyl groups. When sodium alginate dissolves in water, the molecular chains form a viscous spinning solution through hydrogen bonding and electrostatic interactions. Calcium chloride, as a crosslinking agent, allows its calcium ions to coordinate with the carboxyl groups on the sodium alginate molecular chains, forming a primary crosslinking network with an "egg-box" structure, imparting initial gel properties to the spinning solution. The addition of the organosilicon-phospholipid copolymer further enhances this process: the phosphate groups in its molecular chains coordinate with the carboxyl groups and calcium ions of sodium alginate, forming secondary crosslinking points in the gaps of the "egg-box" structure, increasing the crosslinking density; simultaneously, the hydrophobic organosilicon segments of the copolymer tend to aggregate on the fiber surface, forming a hydrophobic barrier and reducing the penetration of salt ions into the fiber interior. The zwitterionic polymer interacts electrostatically with surfactant molecules in the detergent: its anionic groups neutralize cationic surfactants (such as quaternary ammonium salts), and its cationic groups neutralize anionic surfactants (such as alkyl sulfates), thereby reducing the stripping effect of surfactants on the "egg-box" crosslinked structure. Furthermore, the addition of emulsifiers improves the dispersibility of the organosilicon-phospholipid copolymer (hydrophobic segments) and the zwitterionic polymer (polar groups) in sodium alginate solution, avoiding spinning defects caused by phase separation and ensuring the uniformity of the fiber cross-section. Finally, through spinning, crosslinking with calcium chloride solution, and washing and drying, seaweed fibers with a stable "egg-box" structure, resistance to salt ion penetration, and resistance to detergent damage are formed.
[0026] According to a preferred embodiment of the present invention, in step S1, the stirring time at 60-64°C is 2-4 hours; the stirring time is continued for 1-2 hours.
[0027] According to a preferred embodiment of the present invention, in step S2, the soaking time in deionized water is 24-30 hours; the vacuum drying time at 60-64°C is 2-4 hours.
[0028] The present invention also provides an application of the salt-resistant and detergent-resistant seaweed fiber described above or the salt-resistant and detergent-resistant seaweed fiber prepared by the preparation method described above in clothing.
[0029] The beneficial effects of this invention are as follows:
[0030] This invention utilizes the synergistic design and process optimization of bifunctional modified compounds to achieve a systematic improvement in salt resistance, detergent resistance, and overall performance of seaweed fibers, providing a novel material solution for the apparel industry that combines functionality and durability. Addressing the core issue of insufficient salt resistance in traditional seaweed fibers, this invention introduces an organosilicon-phospholipid copolymer to construct a dual protection mechanism. The hydrophobic organosilicon segments of this copolymer form a dense interfacial barrier on the fiber surface, effectively blocking the penetration pathway of salt ions into the material's interior. Simultaneously, the phospholipid groups it contains can chemically react with the polar groups of the sodium alginate molecular chain and external calcium ions to form a stable cross-linked network, enhancing the density of the fiber's internal structure and its resistance to ionic erosion. This synergistic effect of "physical barrier-chemical cross-linking" fundamentally inhibits the damage of salt ions to the fiber structure, significantly improving the material's stability in high-salt environments.
[0031] The introduction of zwitterionic polymers played a crucial role in optimizing detergent resistance. These polymer molecules possess both positive and negatively charged groups, allowing them to electrostatically interact with surfactant molecules in detergents, reducing their ability to peel off the "egg-box" cross-linked structure of seaweed fibers. Simultaneously, the hydrophilic nature of zwitterions regulates the swelling balance of the fibers in different environments, preventing excessive expansion or contraction due to detergent penetration. This dual inhibition of surfactant-induced damage effectively maintains the integrity of the fiber structure, enabling it to retain good mechanical properties and service life even under complex washing conditions.
[0032] From the perspective of overall performance synergy, the combination of components in the formulation further enhances the material's functional performance. Calcium chloride, as a traditional crosslinking agent, forms a basic crosslinking structure with the polar groups of sodium alginate, providing a stable anchoring point for the modifier. The addition of emulsifier improves the dispersibility of the hydrophobic modifier and polar polymer in the spinning solution, avoiding spinning defects caused by phase separation and ensuring the uniformity of fiber cross-section and consistency of mechanical properties. This synergistic effect of multiple components allows the fiber to maintain the biocompatibility and biodegradability of natural seaweed fiber while also taking into account softness and durability. It can better meet the dual requirements of material functionality and comfort in the apparel industry, providing innovative material support for the development of functional clothing. Detailed Implementation
[0033] The following detailed embodiments are only used to further illustrate this application and should not be construed as limiting the scope of protection of this application. Those skilled in the art can make some non-essential improvements and adjustments to this application based on the above application content.
[0034] The following is information on domestic suppliers of the relevant equipment and materials:
[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 2-hydroxyethyl methacrylate 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 Zhenhai Refining & Chemical Branch of China Petroleum & Chemical Corporation.
[0040] The three-necked flask was purchased from Gongyi Yuhua Instrument Co., Ltd.
[0041] The nitrogen gas was purchased from Yingde Gases 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 organosilicon-phospholipid copolymer: 120g of methacryloyloxypropyltrimethoxysilane, 80g of 2-hydroxyethyl methacrylate, and 2g of azobisisobutyronitrile were sequentially added to a three-necked flask containing 300g of toluene. A reflux condenser and thermometer were installed, and nitrogen gas was introduced to purge air from the flask. After 30 minutes, the nitrogen valve was closed. A magnetic stirrer was turned on and stirred at 300 rpm. Simultaneously, the flask was placed in an oil bath and the temperature was slowly increased. When the temperature reached 75℃, the reaction was maintained at a constant temperature for 6 hours. During this period, the temperature and stirring speed were recorded every 30 minutes. Stirring was maintained to ensure the reaction was stable. After the reaction was completed, the oil bath was turned off, and the flask was cooled to room temperature. The reaction solution was then transferred to a rotary evaporator and distilled under reduced pressure at 60°C and -0.09 MPa until the toluene was almost completely removed (about 40 min). The residue after distillation was poured into a beaker, 200 mL of anhydrous ethanol was added and stirred evenly. After standing for 30 min, the mixture was filtered with qualitative filter paper. The filter cake was collected and placed in a vacuum drying oven at 40°C and -0.08 MPa for 12 h to obtain a white powdery organosilicon-phospholipid copolymer.
[0053] Preparation of zwitterionic polymers: Weigh 60g of acrylamide, 30g of 2-acrylamido-2-methylpropanesulfonic acid, and 10g of N-(3-aminopropyl)dimethylallylammonium chloride, and add them sequentially to a glass beaker containing 566.7g of deionized water. Stir with a hand-held stirrer at 200 rpm for 15 minutes until completely dissolved to prepare an aqueous solution with a total solid content of 15%. Transfer the beaker to a constant temperature water bath, set the temperature to 60℃ and maintain it. Purge nitrogen gas to remove oxygen from the solution, and continue for 20 minutes before closing the nitrogen valve. Weigh 0.1g of ammonium persulfate and 0.1g of sodium bisulfite sequentially, dissolve them in a small amount of deionized water, and then add them dropwise. Add the initiator to a beaker and simultaneously increase the stirring speed to 500 rpm. After the initiator is completely dissolved, continue stirring for 5 minutes. Then, raise the water bath temperature to 62°C and maintain the constant temperature for 4 hours. After the reaction is complete, turn off the water bath and let the beaker cool to room temperature. Use a glass rod to pick out the gelatinous product and put it into a tissue homogenizer to homogenize at 1000 rpm for 2 minutes. Pour the resulting fragments into a beaker, add 200 mL of acetone and stir well. After standing for 30 minutes, filter with quantitative filter paper, collect the filter cake and place it in a vacuum drying oven. Set the temperature to 50°C and the vacuum degree to -0.08 MPa and dry for 12 hours to obtain a light yellow granular zwitterionic polymer.
[0054] Preparation of salt- and detergent-resistant seaweed fibers: Weigh 100g of sodium alginate, add 856g of deionized water, pour into a stainless steel reactor equipped with a stirrer, turn on the stirrer and stir at 300 rpm, while heating the reactor to 62℃ and maintaining a constant temperature for 2 hours until the sodium alginate is completely dissolved, obtaining a transparent and viscous spinning solution; add 20g of organosilicon-phospholipid copolymer, 10g of zwitterionic polymer, and 1g of polyethylene glycol octylphenyl ether to the spinning solution in sequence, and continue stirring at 300 rpm for 1 hour until all additives are completely dissolved, obtaining a uniform modified spinning solution; circulate the modified spinning solution through... The fibers were extruded into a calcium chloride solution (a 1% mass fraction solution prepared by dissolving 3g of calcium chloride in 300g of water) at a speed of 0.5 m / min using a spinning machine equipped with a 0.08 mm orifice spinneret. During extrusion, the spinneret was kept 10 cm away from the liquid surface to form a continuous fiber bundle. The fiber bundle was then immersed in deionized water for 24 h (the deionized water was replaced every 8 h to thoroughly remove residual calcium chloride and unreacted modifiers). After immersion, the fibers were removed and placed in a vacuum drying oven at 62℃ and a vacuum of -0.08 MPa for 2 h to obtain light yellowish-brown salt- and detergent-resistant seaweed fibers.
[0055] Example 2
[0056] The specific implementation method is the same as in Example 1, except that the preparation of the organosilicon-phospholipid copolymer is as follows: 130g of methacryloyloxypropyltrimethoxysilane, 70g of 2-hydroxyethyl methacrylate, and 2g of azobisisobutyronitrile are added to a three-necked flask containing 300g of toluene. After purging with nitrogen for 35min, the temperature is raised to 76℃ and reacted for 7h. After the reaction is completed, the toluene is removed by vacuum distillation, the product is precipitated with anhydrous ethanol, filtered, and vacuum dried to obtain the organosilicon-phospholipid copolymer. Preparation of zwitterionic polymer: 55g of acrylamide, 35g of 2-acrylamido-2-methylpropanesulfonic acid, and 10g of N-(3-aminopropyl)dimethylallylammonium chloride were dissolved in 555.6g of deionized water. After purging with nitrogen for 25min to remove oxygen, 0.1g of ammonium persulfate and 0.1g of sodium bisulfite were added sequentially to initiate polymerization. The temperature was raised to 64℃ and the reaction was carried out for 5h. After the reaction was completed, the gel-like product was chopped, precipitated with acetone, filtered, and vacuum dried to obtain zwitterionic polymer. Preparation of salt- and detergent-resistant seaweed fibers: 120g of sodium alginate was added to 826.7g of deionized water and stirred at 64℃ for 3h to obtain a solution; 25g of organosilicon-phospholipid copolymer, 15g of zwitterionic polymer, and 1.5g of polyethylene glycol octylphenyl ether were added sequentially to the sodium alginate solution and stirred for another 1.5h until completely dissolved to obtain a modified spinning solution; the modified spinning solution was extruded through a spinneret into a calcium chloride solution (4g of calcium chloride dissolved in 400g of water) to form fibers; the fibers were soaked in deionized water for 27h (with water changed every 8h) and then vacuum dried at 64℃ for 3h to obtain seaweed fibers.
[0057] Example 3
[0058] The specific implementation method is the same as in Example 1, except that the preparation of the organosilicon-phospholipid copolymer is as follows: 110g of methacryloyloxypropyltrimethoxysilane, 90g of 2-hydroxyethyl methacrylate, and 2g of azobisisobutyronitrile are added to a three-necked flask containing 300g of toluene. After purging with nitrogen for 30min, the temperature is raised to 74℃ and reacted for 8h. After the reaction is completed, the toluene is removed by vacuum distillation, the product is precipitated with anhydrous ethanol, filtered, and vacuum dried to obtain the organosilicon-phospholipid copolymer. Preparation of zwitterionic polymer: 65g of acrylamide, 25g of 2-acrylamido-2-methylpropanesulfonic acid, and 10g of N-(3-aminopropyl)dimethylallylammonium chloride were dissolved in 571.4g of deionized water. After purging with nitrogen for 20min to remove oxygen, 0.1g of ammonium persulfate and 0.1g of sodium bisulfite were added sequentially to initiate polymerization. The temperature was raised to 60℃ and the reaction was carried out for 6h. After the reaction was completed, the gel-like product was chopped, precipitated with acetone, filtered, and vacuum dried to obtain zwitterionic polymer. Preparation of salt- and detergent-resistant seaweed fibers: 150g of sodium alginate was added to 806.7g of deionized water and stirred at 60℃ for 4h to obtain a solution; 15g of organosilicon-phospholipid copolymer, 5g of zwitterionic polymer, and 0.5g of polyethylene glycol octylphenyl ether were added sequentially to the sodium alginate solution and stirred for another 2h until completely dissolved to obtain a modified spinning solution; the modified spinning solution was extruded through a spinneret into a calcium chloride solution (5g of calcium chloride dissolved in 500g of water) to form fibers; the fibers were soaked in deionized water for 30h (with water changed every 8h) and then vacuum dried at 60℃ for 4h to obtain seaweed fibers.
[0059] Comparative Example 1
[0060] The specific implementation method is the same as in Example 1, except that the preparation of salt- and detergent-resistant seaweed fibers is as follows: 100g of sodium alginate is added to 856.7g of deionized water and stirred at 62°C for 2 hours to obtain a solution; 10g of zwitterionic polymer and 1g of polyethylene glycol octylphenyl ether are added sequentially to the sodium alginate solution and stirred for another hour until completely dissolved to obtain a modified spinning solution (without adding organosilicon-phospholipid copolymer); the modified spinning solution is extruded through a spinneret into a calcium chloride solution (3g of calcium chloride dissolved in 300g of water) to form fibers; the fibers are soaked in deionized water for 24 hours (with water changed every 8 hours) and then vacuum dried at 62°C for 2 hours to obtain seaweed fibers.
[0061] Comparative Example 2
[0062] The specific implementation method is the same as in Example 1, except that the preparation of salt- and detergent-resistant seaweed fibers is as follows: 100g of sodium alginate is added to 856.7g of deionized water and stirred at 62°C for 2 hours to obtain a solution; 20g of organosilicon-phospholipid copolymer and 1g of polyethylene glycol octylphenyl ether are added sequentially to the sodium alginate solution and stirred for another hour until completely dissolved to obtain a modified spinning solution (without adding zwitterionic polymers); the modified spinning solution is extruded through a spinneret into a calcium chloride solution (3g of calcium chloride dissolved in 300g of water) to form fibers; the fibers are soaked in deionized water for 24 hours (with water changed every 8 hours), and then vacuum dried at 62°C for 2 hours to obtain seaweed fibers.
[0063] Comparative Example 3
[0064] The specific implementation method is the same as in Example 1, except that the preparation of salt-resistant and detergent-resistant seaweed fiber is as follows: 100g of sodium alginate is added to 886.7g of deionized water and stirred at 62°C for 2 hours to obtain a solution; 1g of polyethylene glycol octylphenyl ether is added to the sodium alginate solution and stirred for another hour until completely dissolved to obtain a modified spinning solution (without adding organosilicon-phospholipid copolymer and zwitterionic polymer); the modified spinning solution is extruded through a spinneret into a calcium chloride solution (3g of calcium chloride dissolved in 300g of water) to form fibers; the fibers are soaked in deionized water for 24 hours (with water changed every 8 hours) and then vacuum dried at 62°C for 2 hours to obtain seaweed fiber.
[0065] Performance testing
[0066] The salt- 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 resistance and detergent resistance, all seaweed fiber samples were equilibrated for 24 hours in a standard temperature and humidity environment (temperature 25℃, relative humidity 65%) to ensure consistent testing conditions. For breaking strength and elongation at break tests: referring to GB / T 1447-2005 "Test Method for Tensile Properties of Fibers", a universal testing machine (accuracy ±1%) was used. Fibers were cut into specimens 200mm in length and 10mm in width, clamped in the machine jaws (clamping distance 20mm), and tested at a tensile rate of 10mm / min. The maximum load (N) at break and the corresponding elongation (mm) were recorded. The breaking strength (cN / dtex, 1cN / dtex = 0.001N / mm × 9000mm / tex) and elongation at break (%, elongation / initial length × 100%) were calculated. Each group of samples was tested 5 times, and the average value was taken. Salt resistance test: The fiber sample was completely immersed in a 3.5% (mass fraction) sodium chloride solution at a constant temperature of 25℃ for 72 hours. After removal, it was rinsed twice with deionized water (5 minutes each time) and dried in a vacuum drying oven at 60℃ until constant weight. The swelling rate was calculated as follows: Swelling rate = [(wet mass after immersion - initial dry mass) / initial dry mass] × 100%; the mass retention rate was calculated as follows: Mass retention rate = [mass after drying / initial dry mass] × 100%. Detergent resistance test: Referring to GB / T 8629-2001 "Technical Requirements for Household Washing Machines for Textiles", a vertical washing machine (capacity 5kg) was used. A standard detergent solution (concentration 0.5%, water temperature 40℃) was prepared, and 50 standard washing cycles were performed (15 minutes each time, spin speed 50 r / min, 3 rinses, spin speed 800 r / min). After washing, the fiber sample was removed, rinsed twice with deionized water, and dried in a vacuum oven at 60℃ until constant weight. The tensile strength of the fibers after washing was tested, and the strength retention rate was calculated as follows: Strength retention rate = [tensile strength after washing / initial tensile strength] × 100%. Simultaneously, the fiber surface morphology was observed using a scanning electron microscope (SEM, accelerating voltage 5kV, magnification 500x) to assess the degree of structural damage. Comprehensive performance evaluation: Combining tensile strength, elongation at break, swelling rate, and strength retention rate after washing, the durability of the fibers in complex environments was comprehensively assessed.
[0068] Performance test results:
[0069] Table 1: Performance test results of each embodiment and comparative example
[0070]
[0071] As can be seen from Table 1, the comparative analysis of Examples 1-3 shows that the present invention effectively solves the technical problems of poor salt resistance and insufficient detergent resistance of traditional seaweed fibers in clothing applications through the synergistic effect of the two modified compounds.
[0072] Regarding salt resistance, traditional seaweed fibers tend to swell excessively and lose mass retention due to the hydroxyl and carboxyl groups on their molecular chains easily binding with salt ions. The organosilicon-phospholipid copolymer added in Examples 1-3 forms a dense barrier through hydrophobic organosilicon segments, reducing the penetration of salt ions into the fiber interior. Its phospholipid groups form additional cross-linking points with sodium alginate carboxyl groups and calcium ions, enhancing the density of the "egg-box" structure. This significantly reduces the swelling rate (12.3±0.5% in Example 1, far lower than 25.1±1.0% in Comparative Example 3) and improves the mass retention rate (92.1±1.0% in Example 1, higher than 82.4±1.5% in Comparative Example 3).
[0073] Regarding detergent resistance, traditional seaweed fibers suffer from a significant decrease in mechanical properties due to the susceptibility of their "egg-box" structure to damage by surfactants in detergents. The zwitterionic polymers added in Examples 1-3 neutralize the electrostatic effects of surfactants through the positive and negative charge groups on their molecular chains, reducing the stripping of the "egg-box" structure. Simultaneously, their hydrophilic properties balance fiber swelling, preventing excessive expansion or contraction. Experimental data show that the retention rates of breaking strength (86.2-87.5%) and breaking elongation (87.8-89.2%) after washing in Examples 1-3 are significantly higher than those in the comparative examples (58.7±3.5% and 61.3±3.0% for Comparative Example 3, respectively). Furthermore, SEM observation shows that the fibers in Examples 1-3 have a dense structure with no obvious damage, while the "egg-box" structure of the fibers in Comparative Example 3 is severely damaged.
[0074] In summary, Examples 1-3, through the synergistic effect of organosilicon-phospholipid copolymer (blocking salt ions and enhancing crosslinking) and zwitterionic polymer (neutralizing surfactants and balancing swelling), simultaneously improve the salt resistance and detergent resistance of the fiber, solving the problems of structural damage and insufficient durability of traditional seaweed fiber in clothing applications caused by environmental factors, and providing technical support for its promotion in the clothing field.
[0075] The embodiments described above are merely examples of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention.
Claims
1. A salt- and detergent-resistant seaweed fiber, characterized by, The raw materials include the following weight parts: Sodium alginate: 50-150 parts by weight; Silicone-phosphorus ester 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 silicone-phosphorus ester copolymer comprises: A1, adding methacryloyloxypropyl trimethoxysilane, methyl methacrylate-2-hydroxyethyl phosphate, and azobisisobutyronitrile into a three-necked flask containing toluene, removing oxygen by nitrogen blowing, and then heating to 74-76℃ for reaction; A2, after the reaction is completed, vacuum distillation is performed, the product is precipitated with anhydrous ethanol, and filtration and vacuum drying are performed; the preparation method of the zwitterionic polymer comprises: B1, dissolving acrylamide, 2-acrylamido-2-methylpropane sulfonic acid, and N-(3-aminopropyl) dimethylallyl ammonium chloride in deionized water, removing oxygen by nitrogen blowing, and then adding ammonium persulfate and sodium bisulfite successively to initiate polymerization, and heating to 60-64℃ for reaction; B2, after the reaction is completed, the gelatinous product is cut into pieces, precipitated with acetone, and then filtered and vacuum dried.
2. The salt and detergent resistant seaweed fiber according to claim 1, characterized by, In step A1, the nitrogen blowing time for oxygen removal is 30-40 min, and the heating time to 74-76℃ for reaction is 6-8 h.
3. The salt and detergent resistant seaweed fiber according to claim 1, characterized by, In step A2, the vacuum drying temperature is 40-42℃, and the time is 12-14 h.
4. The salt and detergent resistant seaweed fiber according to claim 1, characterized by, In step B1, the heating time to 60-64℃ for reaction is 4-6 h.
5. The salt and detergent resistant seaweed fiber according to claim 1, characterized by, In step B2, the vacuum drying temperature is 50-52℃, and the vacuum drying time is 12-14 h.
6. A process for the preparation of salt and detergent resistant seaweed fibres according to any one of claims 1 to 5, characterised by the steps of It comprises: S1, adding sodium alginate into deionized water and stirring at 60-64℃ to obtain a solution; The silicone-phosphorus ester copolymer, the zwitterionic polymer, and the polyethylene glycol octylphenyl ether are sequentially added into the sodium alginate solution, and continue to stir until completely dissolved to obtain a modified spinning solution; 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℃.
7. The preparation method according to claim 6, characterized in that, In step S1, the stirring time at 60-64℃ is 2-4 h, and the continue stirring time is 1-2 h.
8. The preparation method according to claim 6, characterized in that, In step S2, the soaking time in deionized water is 24-30 h, and the vacuum drying time at 60-64℃ is 2-4 h.
9. Use of the salt- and detergent-resistant seaweed fiber according to any one of claims 1 to 5 or the salt- and detergent-resistant seaweed fiber produced by the production method according to any one of claims 6 to 8, characterized in that, The application of the salt-resistant and detergent-resistant seaweed fibers in garments.
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