WO2022237722A1 - 海藻纤维及其制备方法 - Google Patents

海藻纤维及其制备方法 Download PDF

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Publication number
WO2022237722A1
WO2022237722A1 PCT/CN2022/091698 CN2022091698W WO2022237722A1 WO 2022237722 A1 WO2022237722 A1 WO 2022237722A1 CN 2022091698 W CN2022091698 W CN 2022091698W WO 2022237722 A1 WO2022237722 A1 WO 2022237722A1
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Prior art keywords
quaternary ammonium
seaweed
ammonium salt
membered ring
fiber
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PCT/CN2022/091698
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English (en)
French (fr)
Inventor
夏延致
苗大刚
李凯
姚久勇
成芳芳
许长海
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Qingdao University
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Qingdao University
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Priority to EP22806685.8A priority Critical patent/EP4324965B1/en
Priority to KR1020237038297A priority patent/KR102706714B1/ko
Priority to AU2022273103A priority patent/AU2022273103B2/en
Priority to US18/289,896 priority patent/US12366012B2/en
Priority to JP2023570149A priority patent/JP7832614B2/ja
Publication of WO2022237722A1 publication Critical patent/WO2022237722A1/zh
Anticipated expiration legal-status Critical
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/04—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of alginates
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/06—Washing or drying
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/02—Starting the formation
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/02—Chemical after-treatment of artificial filaments or the like during manufacture of cellulose, cellulose derivatives, or proteins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/01—Natural vegetable fibres
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/20—Cellulose-derived artificial fibres

Definitions

  • the application belongs to the technical field of textile fabric dyeing, and in particular relates to a seaweed fiber and a preparation method thereof.
  • Seaweed fiber is a new type of green biodegradable fiber made from sodium alginate extracted from natural seaweed through wet spinning process. It has been valued for its excellent hygroscopic properties, film-forming and fiber-forming properties, as well as good biodegradability and biocompatibility.
  • Seaweed fiber has been widely used in the field of medical dressings, and it also has great potential in high-end clothing, underwear fabrics and decorative textiles.
  • seaweed fiber brings wearing comfort, but also brings difficulty in spinning. On the one hand, it is still difficult to realize purely spun seaweed fiber yarns in the related art. On the other hand, because the current price of seaweed fiber is still slightly higher, so there are more seaweed fiber blended fabrics on the market.
  • seaweed fiber blended with cotton and wool blended are two larger varieties.
  • the fiber after blending can have excellent wearing properties such as antibacterial and flame retardant, making it more suitable for clothing and industrial textiles. Good prospects for industrial application.
  • seaweed fiber the acid-base tolerance of seaweed fiber is poor, and when encountering the solution of ammonium salt, Na+, K+ and H+ ions, the fiber will swell or even dissolve. This has just caused in current dyeing system, seaweed fiber dyeing and its difficulty. The difficulty of dyeing seaweed fiber has become a bottleneck limiting its large-scale application in the textile field.
  • CN101736440A discloses a manufacturing method of dyeable seaweed fiber.
  • the application adds water-soluble dendrimers to the alginate fiber spinning solution, adopts wet spinning equipment and technology, and undergoes Coagulation, stretching, washing and post-processing, to obtain dyeable seaweed fibers.
  • the key of this method is to add polyamide-amine dendrimers in the spinning solution, which cannot solve the strong electronegativity of seaweed fibers, and also needs to add salt to promote dyeing during dyeing, so that it is unavoidable to damage the seaweed fibers. damage.
  • the present application aims to provide a seaweed fiber and a preparation method thereof, so as to solve the technical problem of difficult dyeing of the seaweed fiber existing in the prior art.
  • the application provides a preparation method of seaweed fiber, comprising:
  • At least one or all three of the raw material in S10, the coagulation bath in S20 and the treatment agent in S30 include a five-membered ring quaternary ammonium salt polymer.
  • the five-membered ring quaternary ammonium salt polymer is:
  • R 1 is CH 3 or CH 2 CH 3 or CH 2 (CH 2 ) 4 CH 3 or CH 2 (CH 2 ) 10 CH 3 or CH 2 (CH 2 ) 16 CH 3 or C 6 H 5 CH 2
  • R 2 is CH 3 or CH 2 CH 3 or CH 2 (CH 2 ) 4 CH 3 or CH 2 (CH 2 ) 10 CH 3 or CH 2 (CH 2 ) 16 CH 3 or C 6 H 5 CH 2
  • degree of polymerization n ranges from 50 to 25000.
  • the mass percent content of the five-membered ring quaternary ammonium salt polymer in the seaweed fiber is 0.1% to 10%.
  • S10 specifically includes:
  • the mass percent concentration of sodium alginate in the spinning solution is 3% to 6%.
  • S20 specifically includes:
  • the five-membered ring quaternary ammonium salt polymer comprising a mass percent concentration of 0.01% to 2% is included in the coagulation bath; and/or
  • S40 specifically includes:
  • the treatment agent includes a five-membered ring quaternary ammonium salt polymer, and the mass of the five-membered ring quaternary ammonium salt polymer is 0.5% to 10% of the mass of the seaweed fiber obtained through S30.
  • the pH value of the coagulation bath is 4.5 to 6.5.
  • the coagulation bath is an aqueous calcium chloride solution with a concentration of 1% to 6% by mass.
  • the preparation method also includes:
  • the present application also provides a seaweed fiber, which is obtained by the preparation method in any of the above technical solutions.
  • the preparation method of the seaweed fiber provided by the present application has a high dyeing rate, a low loss rate of the seaweed fiber, and a high soaping fastness. Therefore, the present application can obtain brightly colored seaweed fibers.
  • the preparation method of the seaweed fiber provided by the present application will not destroy the morphological structure of the seaweed fiber, and the seaweed fiber can be dyed in a non-salt and non-alkali system, which can protect the seaweed fiber to the greatest extent.
  • the preparation method of seaweed fiber utilizes spinning crosslinking and post-finishing process, and selects appropriate raw materials, ratios and reaction conditions, etc., to construct quaternary ammonium dyes in the interior and surface of seaweed fiber, and prepare a Dyeing seaweed fiber, so as to solve the current bottleneck problem of seaweed fiber industrial application.
  • Fig. 1 is the scanning electron micrograph of seaweed fiber in the prior art.
  • Fig. 2 is a scanning electron micrograph of the seaweed fiber provided by the present application.
  • the embodiment of the present application provides a preparation method of seaweed fiber, comprising:
  • At least one or all three of the raw material in S10, the coagulation bath in S20 and the treatment agent in S30 include a five-membered ring quaternary ammonium salt polymer.
  • the seaweed fibers of the embodiments of the present application can be used to prepare seaweed fiber blended fabrics, and the seaweed fiber blended fabrics are blended fabrics of seaweed fibers and one or more other fibers.
  • the seaweed fiber blended fabric may be at least one of the following: seaweed fiber/cotton blended fabric, seaweed fiber/viscose blended fabric, seaweed fiber/wool blended fabric, seaweed fiber/cashmere blended fabric, seaweed fiber/silk blended fabric.
  • the seaweed fibers of the embodiments of the present application are easy to dye and have bright colors. It can be dyed by one or more of direct dyes, acid dyes, reactive dyes, natural dyes and indigo dyes.
  • At least one or all three of the raw material in S10, the coagulation bath in S20, and the treatment agent in S30 include the purpose of the five-membered ring quaternary ammonium salt polymer to improve the quality of the seaweed fiber during dyeing.
  • the dye uptake rate of the seaweed fiber blended fabric obtained by the preparation method provided in the examples of the present application is greater than or equal to 85%, and the soaping fastness is greater than or equal to grade 4.
  • Sodium alginate is a block linear polysaccharide composed of two uronic acids with different structures connected by C-1, 4 bonds, namely ⁇ -D-mannuronic acid (referred to as M unit) and ⁇ -L-guro Uronic acid (abbreviated as G unit).
  • M unit ⁇ -D-mannuronic acid
  • G unit ⁇ -L-guro Uronic acid
  • M unit ⁇ -D-mannuronic acid
  • G unit ⁇ -L-guro Uronic acid
  • these two structural units are distributed in the molecular chain in the form of polymannuronic acid (M)n and polyguluronic acid (G)n, with alternating MG or polymeric Alternate (MG)n phase linkage, its chemical structure is as follows:
  • At least one or all three of the raw material in S10, the coagulation bath in S20 and the treatment agent in S30 include a five-membered ring quaternary ammonium salt polymer.
  • a five-membered ring quaternary ammonium salt polymer By adding five-membered ring quaternary ammonium salt polymers in different spinning processes (one or more steps), it is possible to impart dyeable quaternary ammonium dyes to seaweed fibers.
  • the five-membered ring quaternary ammonium salt polymer in the embodiment of the present application has a structure similar to the M unit of seaweed fiber, has better planarity, is easier to adsorb and cross-link with the M unit, and has a lower probability of replacing Ca 2+ .
  • the five-membered ring quaternary ammonium salt polymer in the embodiment of the present application, it can also adsorb different seaweed fiber macromolecular chains, and finally assist the "egg-shell" system to form a stable dyeable seaweed system. At the same time, It can also ensure the stability and mechanical properties of the seaweed fiber as much as possible.
  • the seaweed fibers of the examples of the present application have good dyeability, and can be dyed without salt with commercially available direct dyes.
  • the dyeable seaweed fiber produced by adding the five-membered ring quaternary ammonium salt polymer in the spinning process in the embodiment of the present application has bright color and good fastness. During the dyeing process, the fiber can maintain the original shape, no obvious dissolution phenomenon occurs, and there is no obvious decline in mechanical properties.
  • the five-membered ring quaternary ammonium salt polymer is:
  • R 1 is CH 3 or CH 2 CH 3 or CH 2 (CH 2 ) 4 CH 3 or CH 2 (CH 2 ) 10 CH 3 or CH 2 (CH 2 ) 16 CH 3 or C 6 H 5 CH 2
  • R 2 is CH 3 or CH 2 CH 3 or CH 2 (CH 2 ) 4 CH 3 or CH 2 (CH 2 ) 10 CH 3 or CH 2 (CH 2 ) 16 CH 3 or C 6 H 5 CH 2
  • degree of polymerization n ranges from 50 to 25000.
  • the five-membered ring quaternary ammonium salt polymer is a water-soluble five-membered ring quaternary ammonium salt polymer.
  • the mass percent content of the five-membered ring quaternary ammonium salt polymer in the seaweed fiber is 0.1% to 10%.
  • the mass percent content of the five-membered ring quaternary ammonium salt polymer in the seaweed fiber is 2% to 8%.
  • the mass percent content of the five-membered ring quaternary ammonium salt polymer in the seaweed fiber is 4% to 6%. In some implementations of the examples of the present application, the mass percent content of the five-membered ring quaternary ammonium salt polymer in the seaweed fiber is 5%.
  • the five-membered ring quaternary ammonium salt polymer is prepared by mixing the five-membered ring quaternary ammonium salt monomer, an initiator, and sodium edetate at 60°C to 100°C The temperature is kept at °C for 1h to 5h to obtain the five-membered ring quaternary ammonium salt polymerization.
  • the five-membered ring quaternary ammonium salt polymer is prepared by mixing the five-membered ring quaternary ammonium salt monomer, initiator, sodium edetate, and The temperature is kept at °C for 2h to 3h to obtain the five-membered ring quaternary ammonium salt polymerization.
  • the five-membered ring quaternary ammonium salt polymer is prepared by mixing the five-membered ring quaternary ammonium salt monomer, initiator, and sodium ethylenediamine tetraacetate at 80°C to 85°C The temperature is kept at °C for 2.5 hours to obtain five-membered ring quaternary ammonium salt polymerization.
  • the five-membered ring quaternary ammonium salt polymer is prepared by using a reactor equipped with a stirrer, a thermometer and a nitrogen device.
  • the concentration of the five-membered ring quaternary ammonium salt monomer is 20% to 80%, the concentration of the initiator is 0.1% to 2%, and the sodium edetate is 0.001% to 0.01%.
  • the concentration of the five-membered ring quaternary ammonium salt monomer is 40% to 60%, the concentration of the initiator is 1% to 1.5%, and the sodium edetate is 0.004% to 0.006%.
  • the initiator includes any one of potassium persulfate, sodium persulfate, ammonium persulfate, azobisisobutylamidine hydrochloride, azobisisobutyronitrile, azobisisoheptanonitrile or Several kinds.
  • the specific preparation method for the polymerization of the five-membered ring quaternary ammonium salt is: add a five-membered ring quaternary ammonium salt monomer with a concentration of 20% to 80% in a reactor equipped with a stirrer, a thermometer and a nitrogen device , and then sequentially added: 0.1% to 2% of the initiator, 0.001% to 0.01% of sodium edetate. Then, nitrogen gas is passed for 20 to 40 minutes, and then the temperature is raised to 60 to 100° C., and the temperature is kept for 1 to 5 hours to complete the preparation of the five-membered ring quaternary ammonium salt polymer.
  • S10 specifically includes:
  • S10 specifically includes:
  • S10 specifically includes:
  • the mass percent concentration of sodium alginate in the spinning solution is 3% to 6%.
  • the mass percent concentration of sodium alginate in the spinning solution is 4% to 5%.
  • S20 specifically includes:
  • S20 specifically includes:
  • the coagulation bath includes a five-membered ring quaternary ammonium salt polymer with a concentration of 0.01% to 2% by mass.
  • the coagulation bath includes a five-membered ring quaternary ammonium salt polymer with a concentration of 0.5% to 1.5% by mass.
  • the coagulation bath includes a five-membered ring quaternary ammonium salt polymer with a concentration of 1% by mass.
  • S40 specifically includes:
  • S40 specifically includes:
  • the treatment agent includes a five-membered ring quaternary ammonium salt polymer, and the mass of the five-membered ring quaternary ammonium salt polymer is 0.5% to 10% of the mass of the seaweed fiber obtained through S30.
  • the treatment agent includes a five-membered ring quaternary ammonium salt polymer, and the mass of the five-membered ring quaternary ammonium salt polymer is 2% to 8% of the mass of the seaweed fiber obtained through S30.
  • the treatment agent includes a five-membered ring quaternary ammonium salt polymer, and the mass of the five-membered ring quaternary ammonium salt polymer is 4% to 6% of the mass of the seaweed fiber obtained through S30.
  • the pH of the coagulation bath is 4.5 to 6.5.
  • the pH value of the coagulation bath is 5.
  • the coagulation bath is an aqueous calcium chloride solution with a concentration of 1% to 6% by mass.
  • the coagulation bath is an aqueous calcium chloride solution with a concentration of 2% to 4% by mass.
  • the preparation method further includes:
  • step (3) Dissolve 1g of the five-membered ring quaternary ammonium salt polymer modifier in water to form 1000g of soaking solution; contact the seaweed fiber prepared in step (2) with the soaking solution at 30°C for 20 minutes, and the soaking is completed After washing and drying, post-treatment cross-linked seaweed fibers are obtained.
  • step (3) Dissolve 6g of the five-membered ring quaternary ammonium salt polymer modifier in water to form 1000g of soaking solution; contact the seaweed fiber prepared in step (2) with the soaking solution at 40°C and soak for 10 minutes, and the soaking is completed After washing and drying, post-treatment cross-linked seaweed fibers are obtained.
  • step (3) Dissolve 9g of the five-membered ring quaternary ammonium salt polymer modifier in water to form 6000g of soaking solution; contact the seaweed fiber prepared in step (2) with the soaking solution at 50°C and soak for 8 minutes, and the soaking is completed After washing and drying, post-treatment cross-linked seaweed fibers are obtained.
  • the present invention has adopted non-five-membered ring, common polyquaternary ammonium salt compound has done an embodiment.
  • step (3) Dissolve 1g of diaminocarbamide polymer in water to make 1000g of soaking solution; contact the seaweed fiber prepared in step (2) with the soaking solution at 30°C and soak for 20 minutes, rinse and dry after soaking Obtain post-processing cross-linked seaweed fiber.
  • Fig. 1 is a scanning electron micrograph of a conventional seaweed fiber
  • Fig. 2 is a scanning electron micrograph of a dyeable seaweed fiber.
  • the dyeing properties of ordinary seaweed fibers and the dyeable seaweed fibers obtained in Examples 1, 2, 3 and 4 are shown in Table 1.
  • the dyeing process of the seaweed fiber in the embodiment of the present application is as follows: Weigh 0.2 grams of direct dyes (direct bright red 4BS, direct yellow RS, direct blue 3RL) and add them to 400 grams of water to stir and dissolve, put 10 grams of seaweed fibers at room temperature, and use 2 °C/min temperature rise to 80 °C, after 40 minutes of dyeing. Wash in 5g/l neutral detergent aqueous solution at 90°C for 10 minutes, cool down, wash with water, and dry at 80°C or dry in the air.
  • direct dyes direct bright red 4BS, direct yellow RS, direct blue 3RL
  • seaweed fibers obtained in Examples 1, 2, 3, and 4 have a color fastness to soaping of Direct Scarlet 4BS, Direct Yellow RS, and Direct Blue 3RL that reaches or exceeds Grade 4.
  • references to the terms “one embodiment,” “some embodiments,” “exemplary embodiments,” “example,” “specific examples,” or “some examples” are intended to mean that the implementation A specific feature, structure, material, or characteristic described by an embodiment or example is included in at least one embodiment or example of the present application.
  • schematic representations of the above terms do not necessarily refer to the same embodiment or example.
  • the specific features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

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  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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Abstract

一种海藻纤维及其制备方法，属于纺织织物染色的技术领域。海藻纤维的制备方法包括：S10.采用包括海藻酸钠的原料，制备纺丝液；S20.将通过S10获得的纺丝液挤出至凝固浴进行凝固成型，获得初纤维；S30.对通过S20获得的初纤维进行牵伸和水洗，获得海藻纤维；S40.将通过S30获得的海藻纤维浸入处理剂，进行后处理；其中，S10中的原料、S20中的凝固浴和S30中的处理剂中的至少一者或全部三者包括五元环季胺盐聚合物。上述获得的海藻纤维的上染率较高，纤维强力损伤小，并且皂洗牢度较高。

Description

海藻纤维及其制备方法 技术领域
本申请属于纺织织物染色的技术领域，具体涉及一种海藻纤维及其制备方法。
背景技术
海藻纤维是以天然海藻中提取的海藻酸钠为原料，经湿法纺丝工艺而制成的一种新型绿色生物可降解纤维。因具有优异的吸湿性能、成膜成纤性能，以及良好的生物降解性和生物相容性而得到重视。
海藻纤维目前已在医用敷料领域广泛应用，在高档服装、内衣面料和装饰纺织品方面也具有很大的潜能。
海藻纤维滑爽的手感带来了穿着的舒适性，同时也带来了纺纱的难度。一方面，在相关技术中目前还难以实现海藻纤维纯纺的纱线。另一方面，由于海藻纤维目前的价格还稍高，所以市场上出现比较多就是海藻纤维混纺织物。
其中，海藻纤维与棉混纺和与毛混纺是两个较大的品种，混纺之后的纤维可以兼具抑菌、阻燃等优异的服用性能，使其在服装用及产业用纺织品领域均具有较好的产业化应用前景。
然而，海藻纤维酸碱耐受力较差，并且在遇到铵盐、Na+、K+和H+离子的溶液时，纤维会发生溶胀，甚至溶解。这就致使了在现行染色体系内，海藻纤维染色及其困难。海藻纤维难以染色的问题，成为了限制其在纺织领域大规模应用的瓶颈。
在相关技术中，CN101736440A公开了一种可染海藻纤维的制造方法，该申请案将水溶性的树状大分子添加到海藻酸盐纤维纺丝溶液中，采用湿法纺丝设备和工艺，经凝固、牵伸、水洗和后处理,得到可染色的海藻纤维。该方法的关键是在纺丝液中加入聚酰胺-胺树状大分子，这就不能解决海藻纤维较强的电负性，染色的时候还需要加盐促染，这样就不能避免对海藻纤维的损伤。
此外，如邵欢迎等人发表的论文海藻酸钙纤维的直接染料无盐染色(印染，2014年10月，1-5)和刘杰等人发表的论文海藻酸纤维活性染料染色工艺研究(染整技术，2014年3月，11-13)报道了海藻纤维的制备方法。两篇论文中都用了氯化钙，前者用其做了固色剂，后者用其做了促染剂。氯化钙做固色剂会使纤维变得脆化、易断。氯化钙作为促染剂使用，就像论文中提到的一样，强力损失非常大，下降约30％-40％。
目前也有一些棉无盐染色的工艺由于种种限制也不能用于海藻纤维染色。如CN108914630A，其预处理液烧碱浓度为2-6g/L，此工艺会使海藻纤维基本溶解。如CN106498770A，棉的改性过程中使用是吸附型阳离子改性剂，未使用烧碱。但是明显的线性季铵盐大分子，与海藻纤维的吸附交联效果较差，也会使海藻纤维发生溶胀溶解，影响海藻纤维的使用性能。
综上，本领域的技术人员亟需找到一种可以同时解决海藻纤维染色难的问题，且不会破坏海藻纤维的形态结构，且不会降低海藻纤维的强度的制备方法。
发明内容
本申请旨在提供一种海藻纤维及其制备方法，以解决现有技术中存在的海藻纤维染色难的技术问题。
为了解决上述技术问题，本申请是这样实现的：
本申请提供了一种海藻纤维的制备方法，包括：
S10.采用包括海藻酸钠的原料，制备纺丝液；
S20.将通过S10获得的纺丝液挤出至凝固浴进行凝固成型，获得初纤维；
S30.对通过S20获得的初纤维进行牵伸和水洗，获得海藻纤维；
S40.将通过S30获得的海藻纤维浸入处理剂，进行后处理；
其中，S10中的原料、S20中的凝固浴和S30中的处理剂中的至少一者或全部三者包括五元环季胺盐聚合物。
另外，本发明上述实施例提供的技术方案还可以具有如下附加技术特征：
上述技术方案中，五元环季胺盐聚合物为：
Figure PCTCN2022091698-appb-000001
其中，R 1为CH 3或CH 2CH 3或CH 2(CH 2) 4CH 3或CH 2(CH 2) 10CH 3或CH 2(CH 2) 16CH 3或C 6H 5CH 2，R 2为CH 3或CH 2CH 3或CH 2(CH 2) 4CH 3或CH 2(CH 2) 10CH 3或CH 2(CH 2) 16CH 3或C 6H 5CH 2，聚合度n的范围为50至25000。
上述任一技术方案中，五元环季胺盐聚合物在海藻纤维中的质量百分比含量为0.1％至10％。
上述任一技术方案中，S10具体包括：
S101.按海藻酸钠：五元环季胺盐聚合物＝100：(0.001-30)的质量比，将海藻酸钠和五元环季胺盐聚合物在水中混合，获得纺丝液。
上述任一技术方案中，纺丝液中海藻酸钠的质量百分比浓度为3％至6％。
上述任一技术方案中，S20具体包括：
S201.将通过S10获得的纺丝液在静置脱泡后挤出至温度为40℃至70℃的凝固浴进行凝固成型；
其中，凝固浴中包括质量百分比浓度为0.01％至2％的五元环季胺盐聚合物；和/或
上述任一技术方案中，S40具体包括：
S401.将通过S30获得的海藻纤维浸入温度为20℃至70℃的处理剂，进行时间为5min至60min的后处理；
其中，处理剂中包括五元环季胺盐聚合物，五元环季胺盐聚合物的质量为通过S30获得的海藻纤维的质量的0.5％至10％。
上述任一技术方案中，在S20中，凝固浴的pH值为4.5至6.5。
上述任一技术方案中，在S20中，凝固浴为质量百分比浓度为1％至6％的氯化钙水溶液。
上述任一技术方案中，在S40后，制备方法还包括：
S50.对通过S40获得的海藻纤维进行洗涤处理和烘干处理。
本申请还提供了一种海藻纤维，海藻纤维采用如上述任一技术方案中的制备方法获得。
本申请的有益效果为：
首先，本申请提供的海藻纤维的制备方法上染率较高，海藻纤维损失率低，并且皂洗牢度较高。 因此，本申请能够获得色泽鲜艳的海藻纤维。
此外，本申请提供的海藻纤维的制备方法不会破坏海藻纤维的形态结构，海藻纤维在非盐、非碱体系中就能实现染色，最大程度的保护海藻纤维。
最后，本申请提供的海藻纤维的制备方法利用纺丝交联，以及后整理工艺，并选择合适的原料、比例和反应条件等，在海藻纤维的内部和表面构造出季铵基染坐，制备出可染海藻纤维，从而解决目前海藻纤维产业化应用瓶颈问题。
本申请的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本申请的实践了解到。
附图说明
图1为现有技术中海藻纤维的扫描电镜图。
图2为本申请提供的海藻纤维的扫描电镜图。
具体实施方式
下面通过参考附图描述的实施例是示例性的，仅用于解释本申请，而不能理解为对本申请的限制。基于本申请中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
本申请实施例提供了一种海藻纤维的制备方法，包括：
S10.采用包括海藻酸钠的原料，制备纺丝液；
S20.将通过S10获得的纺丝液挤出至凝固浴进行凝固成型，获得初纤维；
S30.对通过S20获得的初纤维进行牵伸和水洗，获得海藻纤维；
S40.将通过S30获得的海藻纤维浸入处理剂，进行后处理；
其中，S10中的原料、S20中的凝固浴和S30中的处理剂中的至少一者或全部三者包括五元环季胺盐聚合物。
在上述实施例中，可采用本申请实施例的海藻纤维制备海藻纤维混纺织物，海藻纤维混纺织物为海藻纤维与其他一种或多种纤维的混纺织物。比如，海藻纤维混纺织物可以为以下至少之一：海藻纤维/棉混纺织物、海藻纤维/粘胶混纺织物、海藻纤维/羊毛混纺织物、海藻纤维/羊绒混纺织物、海藻纤维/丝绸混纺织物。
在上述实施例中，本申请实施例的海藻纤维易于染色，色彩鲜艳。其可以选择直接染料、酸性染料、活性染料、天然染料、靛蓝染料中的一种或几种进行染色。
在上述实施例中，S10中的原料、S20中的凝固浴和S30中的处理剂中的至少一者或全部三者包括五元环季胺盐聚合物的目的在于，提高海藻纤维在染色时的上染率，降低海藻纤维的损失率，并提高海藻纤维的皂洗牢度。本申请实施例提供的制备方法获得的海藻纤维混纺织物的上染率大于或等于85％，皂洗牢度大于或等于4级。
本申请实施例能够实现上述目的的原理如下。海藻酸钠是由两种结构不同的糖醛酸通过C-1，4键连接而组成的嵌段线形多糖，即β-D-甘露糖醛酸(简称M单元)和α-L-古罗糖醛酸(简称G单元)。海藻酸钠分子中这两种结构单元以多聚甘露糖醛酸(M)n和多聚古罗糖醛酸(G)n的形式分布于分子链中，两者中间以交替MG或多聚交替(MG)n相连接，其化学结构如下：
Figure PCTCN2022091698-appb-000002
当海藻酸钠纺丝液遇到含氯化钙的凝固浴，其会快速地转变成非水溶的海藻酸钙凝胶。这一过程主要是GG链段与Ca 2+产生“蛋-壳”结构，从而产生了海藻纤维。很多一价盐破坏海藻纤维的稳定性，即破坏了其“蛋-壳”交联结构。
本申请的关键之一在于：S10中的原料、S20中的凝固浴和S30中的处理剂中的至少一者或全部三者包括五元环季胺盐聚合物。通过在纺丝的不同过程(一个或多个步骤)中添加五元环季胺盐聚合物，能够赋予海藻纤维可染的季铵基染坐。本申请实施例的五元环季胺盐聚合物，其结构跟海藻纤维M单元类似，有较好的平面性，其较容易的与M单元吸附交联，置换Ca 2+的几率较低。由于本申请实施例的五元环季胺盐聚合物阳离子密度较高，其还可以吸附不同海藻纤维大分子链，最终协助“蛋-壳”体系，形成一个稳定的可染海藻体系，同时，又能够尽可能地保证海藻纤维的稳定性和力学性能。
综上，本申请实施例的海藻纤维具有良好的可染性能，可用商品化的直接染料进行无盐染色。本申请实施例经过纺丝过程中添加五元环季胺盐聚合物生产的可染海藻纤维，其染色色泽鲜艳，牢度好。染色过程中纤维可以保持原有形貌，无明显溶解现象发生，力学性能没有明显的下降。
此外，与例如CN101736440A的相关技术提出的可染海藻纤维的制备方法相比，由于该相关技术把树状大分子加入到纺丝原料中，提供了染坐，但是不能解决纤维电负性的问题。本申请实施例在纺丝过程及后处理过程中，加入了五元环季胺盐聚合物解决了可染海藻纤维稳定的染坐以及电负性的问题。
在本申请实施例的部分实施方式中，五元环季胺盐聚合物为：
Figure PCTCN2022091698-appb-000003
其中，R 1为CH 3或CH 2CH 3或CH 2(CH 2) 4CH 3或CH 2(CH 2) 10CH 3或CH 2(CH 2) 16CH 3或C 6H 5CH 2，R 2为CH 3或CH 2CH 3或CH 2(CH 2) 4CH 3或CH 2(CH 2) 10CH 3或CH 2(CH 2) 16CH 3或C 6H 5CH 2，聚合度n的范围为50至25000。
在本申请实施例的部分实施方式中，五元环季胺盐聚合物为水溶性五元环季胺盐聚合物。
在本申请实施例的部分实施方式中，五元环季胺盐聚合物在海藻纤维中的质量百分比含量为0.1％至10％。
在本申请实施例的部分实施方式中，五元环季胺盐聚合物在海藻纤维中的质量百分比含量为2％至8％。
在本申请实施例的部分实施方式中，五元环季胺盐聚合物在海藻纤维中的质量百分比含量为4％至6％。在本申请实施例的部分实施方式中，五元环季胺盐聚合物在海藻纤维中的质量百分比含量为5％。
在本申请实施例的部分实施方式中，五元环季胺盐聚合物通过以下方式制备：将五元环季胺盐单体、引发剂、乙二胺四乙酸钠混合，在60℃至100℃的温度条件下保温1h至5h，获得五元环季胺盐聚合。
在本申请实施例的部分实施方式中，五元环季胺盐聚合物通过以下方式制备：将五元环季胺盐单体、引发剂、乙二胺四乙酸钠混合，在70℃至90℃的温度条件下保温2h至3h，获得五元环季胺盐聚合。
在本申请实施例的部分实施方式中，五元环季胺盐聚合物通过以下方式制备：将五元环季胺盐单体、引发剂、乙二胺四乙酸钠混合，在80℃至85℃的温度条件下保温2.5h，获得五元环季胺盐聚合。
在上述实施方式中，采用装有搅拌器，温度计和通氮气装置的反应器制备五元环季胺盐聚合物。
在上述实施方式中，五元环季胺盐单体的浓度为20％至80％，引发剂的浓度为0.1％至2％，乙二胺四乙酸钠0.001％至0.01％。
在上述实施方式中，五元环季胺盐单体的浓度为40％至60％，引发剂的浓度为1％至1.5％，乙二胺四乙酸钠0.004％至0.006％。
在上述实施方式中，引发剂包括过硫酸钾、过硫酸钠、过硫酸铵、偶氮二异丁脒盐酸盐、偶氮二异丁腈、偶氮二异庚腈中的任一种或几种。
在上述实施方式中，五元环季胺盐聚合的具体制备方式为：在装有搅拌器，温度计和通氮气装置的反应器中加入浓度20％至80％的五元环季胺盐单体，再依次加入：0.1％至2％的引发剂，0.001％至0.01％的乙二胺四乙酸钠。然后再通氮气20至40分钟后升温到60至100℃，保温1至5小时，完成五元环季胺盐聚合物的制备。
在本申请实施例的部分实施方式中，S10具体包括：
S101.按海藻酸钠：五元环季胺盐聚合物＝100：(0.001-30)的质量比，将海藻酸钠和五元环季胺盐聚合物在水中混合，获得纺丝液。
在本申请实施例的部分实施方式中，S10具体包括：
S101.按海藻酸钠：五元环季胺盐聚合物＝100：(10-20)的质量比，将海藻酸钠和五元环季胺盐聚合物在水中混合，获得纺丝液。
在本申请实施例的部分实施方式中，S10具体包括：
S101.按海藻酸钠：五元环季胺盐聚合物＝100：(12-18)的质量比，将海藻酸钠和五元环季胺盐聚合物在水中混合，获得纺丝液。
在本申请实施例的部分实施方式中，纺丝液中海藻酸钠的质量百分比浓度为3％至6％。
在本申请实施例的部分实施方式中，纺丝液中海藻酸钠的质量百分比浓度为4％至5％。
在本申请实施例的部分实施方式中，S20具体包括：
S201.将通过S10获得的纺丝液在静置脱泡后挤出至温度为40℃至70℃的凝固浴进行凝固成型。
在本申请实施例的部分实施方式中，S20具体包括：
S201.将通过S10获得的纺丝液在静置脱泡后挤出至温度为50℃至60℃的凝固浴进行凝固成型。
在本申请实施例的部分实施方式中，凝固浴中包括质量百分比浓度为0.01％至2％的五元环季胺盐聚合物。
在本申请实施例的部分实施方式中，凝固浴中包括质量百分比浓度为0.5％至1.5％的五元环季胺盐聚合物。
在本申请实施例的部分实施方式中，凝固浴中包括质量百分比浓度为1％的五元环季胺盐聚合物。
在本申请实施例的部分实施方式中，S40具体包括：
S401.将通过S30获得的海藻纤维浸入温度为20℃至70℃的处理剂，进行时间为5min至60min的后处理。
在本申请实施例的部分实施方式中，S40具体包括：
S401.将通过S30获得的海藻纤维浸入温度为40℃至50℃的处理剂，进行时间为20min至40min的后处理。
在本申请实施例的部分实施方式中，处理剂中包括五元环季胺盐聚合物，五元环季胺盐聚合物的质量为通过S30获得的海藻纤维的质量的0.5％至10％。
在本申请实施例的部分实施方式中，处理剂中包括五元环季胺盐聚合物，五元环季胺盐聚合物的质量为通过S30获得的海藻纤维的质量的2％至8％。
在本申请实施例的部分实施方式中，处理剂中包括五元环季胺盐聚合物，五元环季胺盐聚合物的质量为通过S30获得的海藻纤维的质量的4％至6％。
在本申请实施例的部分实施方式中，在S20中，凝固浴的pH值为4.5至6.5。
在本申请实施例的部分实施方式中，在S20中，凝固浴的pH值为5。
在本申请实施例的部分实施方式中，在S20中，凝固浴为质量百分比浓度为1％至6％的氯化钙水溶液。
在本申请实施例的部分实施方式中，在S20中，凝固浴为质量百分比浓度为2％至4％的氯化钙水溶液。
在本申请实施例的部分实施方式中，在S40后，制备方法还包括：
S50.对通过S40获得的海藻纤维进行洗涤处理和烘干处理。
实施例1：
(1)将40g海藻酸钠和1g五元环季胺盐聚合物改性剂配成1000g溶液。
(2)配制质量百分比5％的氯化钙+1％的五元环季胺盐聚合物改性剂溶液凝固浴，并用盐酸调节凝固浴pH值至5，将纺丝液静置脱泡后挤出到40℃的凝固浴水溶液中凝固成型，经过牵伸、冲洗。
(3)将1g五元环季胺盐聚合物改性剂溶于水中配成1000g浸泡液；将步骤(2)中制备的海藻纤维与浸泡液30℃下相互接触并浸润20分钟，浸润完成后经冲洗、干燥后得到后处理交联海藻纤维。
实施例2：
(1)将100g海藻酸钠溶于水中配成2000g溶液。
(2)配制质量百分比6％的氯化钙+1.5％的五元环季胺盐聚合物改性剂溶液凝固浴，并用盐酸调节凝固浴pH值至6，将纺丝液静置脱泡后挤出到40℃的凝固浴水溶液中凝固成型，经过牵伸、冲洗；
(3)将6g五元环季胺盐聚合物改性剂溶于水中配成1000g浸泡液；将步骤(2)中制备的海藻纤维与浸泡液40℃下相互接触并浸润10分钟，浸润完成后经冲洗、干燥后得到后处理交联海藻纤维。
实施例3：
(1)将300g海藻酸钠溶于水中配成4000g溶液。
(2)配制质量百分比4.5％的氯化钙溶液凝固浴，并用盐酸调节凝固浴pH值至5，将纺丝液静置脱泡后挤出到55℃的凝固浴水溶液中凝固成型，经过牵伸、冲洗；
(3)将9g五元环季胺盐聚合物改性剂溶于水中配成6000g浸泡液；将步骤(2)中制备的海藻纤维与浸泡液50℃下相互接触并浸润8分钟，浸润完成后经冲洗、干燥后得到后处理交联海藻纤维。
为了对比，本发明采用了非五元环，普通型聚季铵盐化合物做了一个实施例。
实施例4：
(1)将40g海藻酸钠和1g二氨基脲聚合物配成1000g溶液。
(2)配制质量百分比5％的氯化钙+1％的二氨基脲聚合物溶液凝固浴，并用盐酸调节凝固浴pH值至5，将纺丝液静置脱泡后挤出到40℃的凝固浴水溶液中凝固成型，经过牵伸、冲洗。
(3)将1g二氨基脲聚合物溶于水中配成1000g浸泡液；将步骤(2)中制备的海藻纤维与浸泡液30℃下相互接触并浸润20分钟，浸润完成后经冲洗、干燥后得到后处理交联海藻纤维。
图1为常规海藻纤维的扫描电镜图，图2为可染海藻纤维扫描电镜图。普通海藻纤维和实施例1、2、3、4所得到的可染海藻纤维的染色性能如表1所示。
表1普通和可染海藻纤维的性能
Figure PCTCN2022091698-appb-000004
本申请实施例的海藻纤维的染色工艺如下：称取0.2克直接染料(直接大红4BS、直接黄RS、直接蓝3RL)加入到400克水中搅拌溶解,在常温下投入10克海藻纤维,以2℃/min升温到80℃，染色40分钟后。在90℃5g/l的中性洗涤剂水溶液中洗10分钟，降温，水洗，在80℃烘干或者晾干。
参照国家标准《GB/T3921-2008纺织品色牢度试验耐皂洗色牢度》测试纤维的水洗色牢度。实施例1、2、3、4所得海藻纤维对直接大红4BS、直接黄RS、直接蓝3RL的皂洗色牢度均达到或超过4级。
本申请的说明书和权利要求书中的术语“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本申请的描述中，除非另有说明，“多个”的含义是两个或两个以上。此外，说明书以及权利要求中“和/或”表示所连接对象的至少其中之一，字符“/”，一般表示前后关联对象是一种“或”的关系。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示意性实施例”、“示例”、“具体 示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本申请的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
尽管已经示出和描述了本申请的实施例，本领域的普通技术人员可以理解：在不脱离本申请的原理和宗旨的情况下可以对这些实施例进行多种变化、修改、替换和变型，本申请的范围由权利要求及其等同物限定。

Claims (6)

  1. 一种海藻纤维的制备方法，其特征在于，包括：
    S10.按海藻酸钠：五元环季胺盐聚合物＝100：(0.001-30)的质量比，将所述海藻酸钠和所述五元环季胺盐聚合物在水中混合，获得纺丝液；
    S20.将通过所述S10获得的所述纺丝液在静置脱泡后挤出至温度为40℃至70℃的凝固浴进行凝固成型，获得初纤维；
    其中，所述凝固浴中包括质量百分比浓度为0.01％至2％的所述五元环季胺盐聚合物；
    S30.对通过所述S20获得的所述初纤维进行牵伸和水洗，获得所述海藻纤维；
    S40.将通过所述S30获得的所述海藻纤维浸入温度为20℃至70℃的处理剂，进行时间为5min至60min的浸入处理；
    其中，所述处理剂中包括所述五元环季胺盐聚合物，所述五元环季胺盐聚合物的质量为通过所述S30获得的所述海藻纤维的质量的0.5％至10％；
    所述五元环季胺盐聚合物为：
    Figure PCTCN2022091698-appb-100001
    其中，R 1为CH 3或CH 2CH 3或CH 2(CH 2) 4CH 3或CH 2(CH 2) 10CH 3或CH 2(CH 2) 16CH 3或C 6H 5CH 2，R 2为CH 3或CH 2CH 3或CH 2(CH 2) 4CH 3或CH 2(CH 2) 10CH 3或CH 2(CH 2) 16CH 3或C 6H 5CH 2，聚合度n的范围为50至25000。
  2. 根据权利要求1所述的海藻纤维的制备方法，其特征在于，所述五元环季胺盐聚合物在所述海藻纤维中的质量百分比含量为0.1％至10％。
  3. 根据权利要求1所述的海藻纤维的制备方法，其特征在于，所述纺丝液中所述海藻酸钠的质量百分比浓度为3％至6％。
  4. 根据权利要求1至3任一项所述的海藻纤维的制备方法，其特征在于，在所述S20中，所述凝固浴的pH值为4.5至6.5；和/或在所述S20中，所述凝固浴还包括质量百分比浓度为1％至6％的氯化钙水溶液。
  5. 根据权利要求1至3中任一项所述的海藻纤维的制备方法，其特征在于，在所述S40后，所述制备方法还包括：S50.对通过所述S40获得的所述海藻纤维进行洗涤处理和烘干处理。
  6. 一种海藻纤维，其特征在于，所述海藻纤维采用如权利要求1至5中任一项所述的制备方法获得。
PCT/CN2022/091698 2021-05-12 2022-05-09 海藻纤维及其制备方法 Ceased WO2022237722A1 (zh)

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