WO2022252955A1 - Hydroxylated alginate fiber and preparation method therefor - Google Patents

Hydroxylated alginate fiber and preparation method therefor Download PDF

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WO2022252955A1
WO2022252955A1 PCT/CN2022/092530 CN2022092530W WO2022252955A1 WO 2022252955 A1 WO2022252955 A1 WO 2022252955A1 CN 2022092530 W CN2022092530 W CN 2022092530W WO 2022252955 A1 WO2022252955 A1 WO 2022252955A1
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alginate
polyvinyl alcohol
hydroxylated
divalent
water
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PCT/CN2022/092530
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French (fr)
Chinese (zh)
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时留新
孙海燕
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南京林业大学
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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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances

Definitions

  • the invention belongs to the technical field of polymer materials, and in particular relates to a hydroxylated alginic acid fiber and a preparation method thereof.
  • the GG segment contained in the molecular structure of alginic acid can complex with calcium, iron, lead and other metal ions with more than two valences to form a "zigzag structure", forming an insoluble gel with an "eggshell structure".
  • Alginate is a non-toxic, harmless, biodegradable pure natural green material. Sodium alginate is put into the dissolving kettle and dissolved with water to obtain a clear and transparent solution. Under the action of pressure, the solution enters the slurry storage tank through a filter and is defoamed under vacuum to obtain a uniformly mixed spinning stock solution. When spinning, the temperature of the spinning solution is controlled at 40°C.
  • the spinning solution is extruded from the spinneret after passing through the metering pump and filter under pressure, and enters the coagulation bath mainly composed of calcium chloride aqueous solution, and then passes through After stretching, washing, winding and drying, alginate fibers are obtained.
  • the heat resistance of alginate fiber is poor. When heated to 110°C, the fiber starts to turn yellow, and the strength drops significantly.
  • Ca 2+ is hybridized in the SP3 orbital and forms a coordination structure with the GG segment of the sodium alginate structural unit.
  • Two carboxyl oxygens, one glycosidic bond oxygen and one hydroxyl oxygen participate in the coordination, forming an "egg-box""structure.
  • the "egg-box" structure of alginate is directly related to the breaking strength of alginate fiber and this structure. Improving the process conditions makes the fiber bind as much calcium ions as possible, which helps to improve its breaking strength. In fact, the breaking strength of alginate fibers prepared by the above process is still ⁇ 3.25 cN/dtex.
  • the preparation of polyvinyl alcohol fibers adopts PVA wet spinning, which is to dissolve polyvinyl alcohol in water through steps such as washing, dissolving, filtering, and defoaming in the stock solution process to obtain spinning fibers with good spinnability at a certain concentration and temperature.
  • Stock solution the spinning stock solution enters the coagulation bath through the spinneret for desolventization, and the coagulant in the coagulation bath is generally a strong acid salt.
  • the dehydrated tow has a sheath-core structure, and then stretched in an air bath (guide roll stretching), drying, heat treatment and other processes to prepare semi-finished fibers containing 10% to 13% coagulant, and finally washed with low temperature water and rolled in hot water. shrinkage, oiling, chain plate drying and other processes to make polyvinyl alcohol fibers.
  • Alginate fibers have poor mechanical properties, while polyvinyl alcohol fibers have excellent physical properties. Both polyvinyl alcohol and calcium alginate are hydrophilic polymers with good mutual solubility. The two materials are mixed to reduce the PVA fiber skin-core structure by using the physical properties of polyvinyl alcohol and the calcium and sodium response characteristics of alginate. process to produce composite fibers.
  • pure calcium alginate is a tightly cross-linked macromolecule, and the hydrogen bonding force formed with polyvinyl alcohol is weaker than water, and is affected by concentration, volume and shape; the composite fiber produced cannot be obtained Excellent mechanical properties.
  • the technical problem to be solved by the present invention is to provide a preparation method of hydroxylated alginic acid fiber.
  • Another technical problem to be solved by the present invention is to provide a hydroxylated alginic acid fiber.
  • a preparation method of hydroxylated alginic acid fiber which comprises pulverizing divalent alginate, adding it to polyvinyl alcohol aqueous solution after pulverization, and then performing stirring, defoaming, metering, coagulation, drawing and shaping to obtain hydroxylated alginic acid fiber.
  • the preparation method of the hydroxylated alginic acid fiber includes adding an excessive amount of cross-linking agent to the monovalent alginate aqueous solution to carry out a sudden polymerization reaction to form a divalent alginate corresponding to the cross-linking agent;
  • the cross-linking agent is two Valence cations are any one of Ca 2+ , Mg 2+ , Ba 2+ , Cu 2+ , Zn 2+ or Fe 2+ .
  • the sieving particle size of the pulverized divalent alginate is less than 350 ⁇ m.
  • the sieving particle size of the pulverized divalent alginate is less than 20 ⁇ m.
  • the mass ratio of the polyvinyl alcohol to the divalent alginate is 1:99-99:1.
  • the alcoholysis degree of the polyvinyl alcohol is 70%-100%; the polymerization degree of the polyvinyl alcohol is 450-2600.
  • the first coagulation bath for coagulation is an aqueous solution of sodium salt and water; the second coagulation bath for coagulation is an aqueous solution of calcium salt and water.
  • the polyvinyl alcohol is dissolved at high temperature first, and then the pulverized cross-linked alginate is added when the temperature is controlled at 45-55°C; after adding the cross-linked alginate, the subsequent production process is low at 60°C.
  • the preparation method of the hydroxylated alginic acid fiber specifically comprises the following steps:
  • the first step the preparation of the coagulation bath
  • the cross-linking agent is a divalent cation, any one of Ca 2+ , Mg 2+ , Ba 2+ , Cu 2+ , Zn 2+ or Fe 2+ ;
  • the spinning stock solution passes through the metering pump, passes through the spinneret hole diameter of 0.07-0.08 mm, and the spin rate of a single spindle is 180mL/min, and enters the first coagulation bath to form primary fibers.
  • the negative stretch rate in the primary fiber bath is -19%;
  • the godet roll enters the second coagulation bath with a stretching speed of 32m/min, and then goes through the dry heat stretching of 90m/min, and then enters the shaping process, and finally produces hydroxylated alginic acid fibers.
  • the hydroxylated alginate fiber prepared by the above method.
  • the advantages of the present invention include:
  • the present invention physically reduces the volume of the divalent alginate by pulverizing the divalent alginate, adding it to the polyvinyl alcohol aqueous solution, the hydrogen bond angle between the divalent alginate and the polyvinyl alcohol is small, the bond High strength, strong hydrogen bond force, and increased compatibility; the produced fiber has certain physical properties, and the single yarn breaking strength is ⁇ 16.5cN/dtex.
  • water is deionized water, purified water or soft water.
  • the detection method refers to the standard and the microscopic test (GB-T 14337-2008, using optical microscopy and electron microscopy to study the morphology of synthetic fibers).
  • a preparation method of hydroxylated alginic acid fiber comprising the following steps:
  • the first step the preparation of the coagulation bath
  • the spinning stock solution passes through the metering pump, passes through the spinneret hole diameter of 0.08 mm, and the spin rate of a single spindle is 180 mL/min, and enters the first coagulation bath to form primary fibers.
  • the negative stretch rate in the primary fiber bath is -19%.
  • the nascent fiber enters the second coagulation bath with the godet roller, and the extension speed is 32m/min. Through 90m/min dry heat stretching, and then enter into the shaping process to make polyvinyl alcohol/alginic acid fiber.
  • the single yarn breaking strength is 19.7cN/tex.
  • the cross-section of the fiber is waist-circular; there is a relatively obvious skin-core structure, the color of the cortex and the core is obviously different, and the cortex is relatively thin. Transverse striations, covered with darker pits (alginate).
  • a preparation method of hydroxylated alginic acid fiber comprising the following steps:
  • the first step the preparation of the coagulation bath
  • the spinning stock solution passes through the metering pump, passes through the spinneret hole diameter of 0.08 mm, and the spin rate of a single spindle is 180 mL/min, and enters the first coagulation bath to form primary fibers.
  • the negative stretch rate in the primary fiber bath is -19%.
  • the nascent fiber enters the second coagulation bath with the godet roller, and the extension speed is 32m/min. Through 90m/min dry heat stretching, and then enter into the shaping process to make polyvinyl alcohol/alginic acid fiber.
  • the single yarn breaking strength is 18.1CN/tex.
  • the cross-section of the fiber is waist-circular; there is a relatively obvious skin-core structure, the color of the cortex and the core is obviously different, and the cortex is thin. Transverse striations, covered with darker pits (alginate).
  • a preparation method of hydroxylated alginic acid fiber comprising the following steps:
  • the first step the preparation of the coagulation bath
  • the spinning stock solution passes through the metering pump, passes through the spinneret hole diameter of 0.07 mm, and the spin rate of a single spindle is 180 mL/min, and enters the first coagulation bath to form primary fibers.
  • the negative stretch rate in the primary fiber bath is -19%.
  • the nascent fiber enters the second coagulation bath with the godet roller, and the extension speed is 32m/min. Through 90m/min dry heat stretching, and then enter into the shaping process to make polyvinyl alcohol/alginic acid fiber.
  • the single yarn breaking strength is 16.7CN/tex.
  • the cross-section of the fiber is waist-circular; there is a relatively obvious skin-core structure, the color of the cortex and the core is obviously different, and the cortex is thin. Transverse striations, covered with darker pits (alginate).

Abstract

A hydroxylated alginate fiber and a preparation method therefor, belonging to the technical field of polymer materials. The method comprises: pulverizing divalent alginate, adding the pulverized product to a polyvinyl alcohol aqueous solution, and then stirring, deaerating, measuring, coagulating, drawing and shaping to obtain a hydroxylated alginate fiber. By means of the method for pulverizing the divalent alginate, the volume of the divalent alginate is physically reduced, and same is added to the polyvinyl alcohol aqueous solution, so that the hydrogen bond angle between the divalent alginate and the polyvinyl alcohol is small, the bond strength is large, the hydrogen bond force is strong, and the compatibility is increased. The produced fiber has certain physical properties, and the breaking strength of single yarn is ≥16.5 cN/dtex.

Description

一种羟基化海藻酸纤维及其制备方法A kind of hydroxylated alginic acid fiber and its preparation method 技术领域technical field
本发明属于高分子材料技术领域，具体涉及一种羟基化海藻酸纤维及其制备方法。The invention belongs to the technical field of polymer materials, and in particular relates to a hydroxylated alginic acid fiber and a preparation method thereof.
背景技术Background technique
海藻酸分子结构中含有的GG片段，可与钙、铁、铅等二价以上的金属离子络合生成“锯齿型结构”，形成“蛋壳结构”的不溶性凝胶。海藻酸盐是一种无毒、无害、可生物降解的纯天然绿色材料。将海藻酸钠投放于溶解釜内，加水溶解，得到清澈透明的溶液，在压力的作用下，溶液经过滤器进入贮浆桶，并于真空下脱泡，制得混合均匀的纺丝原液。纺丝时，控制纺丝液的温度在40℃，纺丝原液在压力作用下经过计量泵、过滤器后从喷丝头挤出，进入主要由氯化钙水溶液组成的凝固浴中，再经过拉伸、水洗、卷绕、干燥后便得到海藻酸盐纤维。海藻酸盐纤维的耐热性较差，加热至110℃时，纤维开始发黄，而且强度下降明显。The GG segment contained in the molecular structure of alginic acid can complex with calcium, iron, lead and other metal ions with more than two valences to form a "zigzag structure", forming an insoluble gel with an "eggshell structure". Alginate is a non-toxic, harmless, biodegradable pure natural green material. Sodium alginate is put into the dissolving kettle and dissolved with water to obtain a clear and transparent solution. Under the action of pressure, the solution enters the slurry storage tank through a filter and is defoamed under vacuum to obtain a uniformly mixed spinning stock solution. When spinning, the temperature of the spinning solution is controlled at 40°C. The spinning solution is extruded from the spinneret after passing through the metering pump and filter under pressure, and enters the coagulation bath mainly composed of calcium chloride aqueous solution, and then passes through After stretching, washing, winding and drying, alginate fibers are obtained. The heat resistance of alginate fiber is poor. When heated to 110°C, the fiber starts to turn yellow, and the strength drops significantly.
Ca 2+以SP3轨道杂化，与海藻酸钠结构单元的GG段形成了配位结构，2个羧基氧、1个糖苷键氧和1个羟基氧参与了配位，形成了“egg-box”结构。海藻酸盐“egg-box”结构与海藻酸盐纤维的断裂强度和这种结构直接相关，改善工艺条件使纤维结合尽可能多的钙离子，有助于提高其断裂强度。事实上，通过上述工艺制备的海藻酸盐纤维的断裂强度仍≤3.25cN/dtex。 Ca 2+ is hybridized in the SP3 orbital and forms a coordination structure with the GG segment of the sodium alginate structural unit. Two carboxyl oxygens, one glycosidic bond oxygen and one hydroxyl oxygen participate in the coordination, forming an "egg-box""structure. The "egg-box" structure of alginate is directly related to the breaking strength of alginate fiber and this structure. Improving the process conditions makes the fiber bind as much calcium ions as possible, which helps to improve its breaking strength. In fact, the breaking strength of alginate fibers prepared by the above process is still ≤3.25 cN/dtex.
聚乙烯醇纤维的制备采用PVA湿法纺丝，是在原液工序通过水洗、溶解、过滤、脱泡等步骤将聚乙烯醇溶解于水中制得一定浓度和温度的具有良好可纺性的纺丝原液，纺丝原液通过喷丝头进入凝固浴中进行脱溶剂，凝固浴中的凝固剂一般为强酸盐。经过脱水的丝束为皮芯结构，再经空气浴拉伸(导辊拉伸)、干燥、热处理等工序制得含10％～13％凝固剂的半成品纤维，最后经低温水洗、热水卷缩、上油、链板干燥等工序制成聚乙烯醇纤维。The preparation of polyvinyl alcohol fibers adopts PVA wet spinning, which is to dissolve polyvinyl alcohol in water through steps such as washing, dissolving, filtering, and defoaming in the stock solution process to obtain spinning fibers with good spinnability at a certain concentration and temperature. Stock solution, the spinning stock solution enters the coagulation bath through the spinneret for desolventization, and the coagulant in the coagulation bath is generally a strong acid salt. The dehydrated tow has a sheath-core structure, and then stretched in an air bath (guide roll stretching), drying, heat treatment and other processes to prepare semi-finished fibers containing 10% to 13% coagulant, and finally washed with low temperature water and rolled in hot water. shrinkage, oiling, chain plate drying and other processes to make polyvinyl alcohol fibers.
海藻酸盐纤维力学性能较差，聚乙烯醇纤维有着优良的物理性能。聚乙烯醇和海藻酸钙均为亲水性聚合物，互溶性好，将两种材料混合，利用聚乙烯醇的物理性能和海藻酸盐的钙、钠响应的特性减少PVA纤维皮芯结构，通过工艺，生产出复合纤维。但是，单纯的海藻酸钙是一个交联紧密的大分子，与聚乙烯醇形成的氢键作用力相对水而言较弱，并受浓度、体积和形态的影响；生产得到的复合纤维无法得到优良的力学性能。Alginate fibers have poor mechanical properties, while polyvinyl alcohol fibers have excellent physical properties. Both polyvinyl alcohol and calcium alginate are hydrophilic polymers with good mutual solubility. The two materials are mixed to reduce the PVA fiber skin-core structure by using the physical properties of polyvinyl alcohol and the calcium and sodium response characteristics of alginate. process to produce composite fibers. However, pure calcium alginate is a tightly cross-linked macromolecule, and the hydrogen bonding force formed with polyvinyl alcohol is weaker than water, and is affected by concentration, volume and shape; the composite fiber produced cannot be obtained Excellent mechanical properties.
发明内容Contents of the invention
针对现有技术中存在的问题，本发明要解决的技术问题在于提供一种羟基化海藻酸纤维的制备方法。本发明要解决的另一个技术问题在于提供一种羟基化海藻酸纤维。Aiming at the problems existing in the prior art, the technical problem to be solved by the present invention is to provide a preparation method of hydroxylated alginic acid fiber. Another technical problem to be solved by the present invention is to provide a hydroxylated alginic acid fiber.
为了解决上述问题，本发明所采用的技术方案如下：In order to solve the above problems, the technical scheme adopted in the present invention is as follows:
一种羟基化海藻酸纤维的制备方法，将二价海藻酸盐进行粉碎，粉碎后添加到聚乙烯醇水溶液中，再进行搅拌、脱泡、计量、凝固、牵伸和定型，得到羟基化海藻酸纤维。A preparation method of hydroxylated alginic acid fiber, which comprises pulverizing divalent alginate, adding it to polyvinyl alcohol aqueous solution after pulverization, and then performing stirring, defoaming, metering, coagulation, drawing and shaping to obtain hydroxylated alginic acid fiber.
所述羟基化海藻酸纤维的制备方法，向一价海藻酸盐水溶液中添加过量的交联剂，进行暴聚反应，形成交联剂对应的二价海藻酸盐；所述交联剂为二价阳离子，为Ca 2+、Mg 2+、Ba 2+、Cu 2+、Zn 2+或Fe 2+中的任一种。 The preparation method of the hydroxylated alginic acid fiber includes adding an excessive amount of cross-linking agent to the monovalent alginate aqueous solution to carry out a sudden polymerization reaction to form a divalent alginate corresponding to the cross-linking agent; the cross-linking agent is two Valence cations are any one of Ca 2+ , Mg 2+ , Ba 2+ , Cu 2+ , Zn 2+ or Fe 2+ .
所述羟基化海藻酸纤维的制备方法，粉碎的二价海藻酸盐筛分粒度＜350μm。In the preparation method of the hydroxylated alginate fiber, the sieving particle size of the pulverized divalent alginate is less than 350 μm.
所述羟基化海藻酸纤维的制备方法，粉碎的二价海藻酸盐筛分粒度＜20μm。In the preparation method of the hydroxylated alginic acid fiber, the sieving particle size of the pulverized divalent alginate is less than 20 μm.
所述羟基化海藻酸纤维的制备方法，所述聚乙烯醇与二价海藻酸盐的质量比为1:99～99:1。In the preparation method of the hydroxylated alginic acid fiber, the mass ratio of the polyvinyl alcohol to the divalent alginate is 1:99-99:1.
所述羟基化海藻酸纤维的制备方法，所述聚乙烯醇的醇解度为70％～100％；聚乙烯醇的聚合度为450～2600。In the preparation method of the hydroxylated alginic acid fiber, the alcoholysis degree of the polyvinyl alcohol is 70%-100%; the polymerization degree of the polyvinyl alcohol is 450-2600.
所述羟基化海藻酸纤维的制备方法，所述凝固的第一凝固浴为钠盐与水的水溶液；凝固的第二凝固浴为钙盐与水的水溶液。In the preparation method of the hydroxylated alginic acid fiber, the first coagulation bath for coagulation is an aqueous solution of sodium salt and water; the second coagulation bath for coagulation is an aqueous solution of calcium salt and water.
所述羟基化海藻酸纤维的制备方法，先将聚乙烯醇高温溶解，温度控制在45～55℃时再添加粉碎过的交联海藻酸盐；添加交联海藻酸盐后，后续生产工艺低于60℃。In the preparation method of the hydroxylated alginate fiber, the polyvinyl alcohol is dissolved at high temperature first, and then the pulverized cross-linked alginate is added when the temperature is controlled at 45-55°C; after adding the cross-linked alginate, the subsequent production process is low at 60°C.
所述羟基化海藻酸纤维的制备方法，具体包括以下步骤：The preparation method of the hydroxylated alginic acid fiber specifically comprises the following steps:
第一步，凝固浴的制备The first step, the preparation of the coagulation bath
称取钠盐和水，制备第一凝固浴；称取钙盐和水，制备第二凝固浴；其中第一凝固浴的浓度为30～40wt.％，第二凝固浴的浓度为4～5.5wt.％；Weigh sodium salt and water to prepare the first coagulation bath; weigh calcium salt and water to prepare the second coagulation bath; wherein the concentration of the first coagulation bath is 30-40wt.%, and the concentration of the second coagulation bath is 4-5.5 wt.%;
第二步，粉碎Step two, smash
将一价海藻酸盐加入水中，搅拌均匀后加入交联剂，形成二价海藻酸盐凝胶；将含有水的二价海藻酸盐凝胶高速粉碎，粉碎至二价海藻酸盐的筛分粒度＜350μm；所述交联剂为二价阳离子，为Ca 2+、Mg 2+、Ba 2+、Cu 2+、Zn 2+或Fe 2+中的任一种； Add monovalent alginate into water, stir evenly and add cross-linking agent to form divalent alginate gel; crush the divalent alginate gel containing water at high speed, and crush until the sieving of divalent alginate Particle size <350 μm; the cross-linking agent is a divalent cation, any one of Ca 2+ , Mg 2+ , Ba 2+ , Cu 2+ , Zn 2+ or Fe 2+ ;
第三步，纺丝原液制备The third step, spinning dope preparation
将聚乙烯醇加入水中，加热至温度高于90℃，直至聚乙烯醇完全溶解到水中，形成聚乙烯醇溶液；取上述聚乙烯醇溶液，温度控制在45～55℃，加入粉碎后并带有水的二价海藻酸盐，搅拌均匀，形成纺丝原液；所述聚乙烯醇的醇解度为70％～100％；聚乙烯醇的聚合度为450～2600；聚乙烯醇溶液的浓度为10～20wt.％；Add polyvinyl alcohol into water, heat to a temperature higher than 90°C until the polyvinyl alcohol is completely dissolved in water to form a polyvinyl alcohol solution; take the above polyvinyl alcohol solution, control the temperature at 45-55°C, add it and crush it and bring The divalent alginate with water is stirred evenly to form a spinning stock solution; the degree of alcoholysis of the polyvinyl alcohol is 70% to 100%; the degree of polymerization of the polyvinyl alcohol is 450 to 2600; the concentration of the polyvinyl alcohol solution 10-20wt.%;
第四步，纺丝The fourth step, spinning
纺丝原液通过计量泵，通过喷丝孔径0.07～0.08毫米，单锭吐丝量180mL/min，进入第一凝固浴，形成初生纤维，初生纤维浴中负拉伸率-19％；初生纤维随导丝辊进入第二凝固浴， 延伸速度在32m/min，通过90m/min的干热延伸，再进入定型工序，最后制成羟基化海藻酸纤维。The spinning stock solution passes through the metering pump, passes through the spinneret hole diameter of 0.07-0.08 mm, and the spin rate of a single spindle is 180mL/min, and enters the first coagulation bath to form primary fibers. The negative stretch rate in the primary fiber bath is -19%; The godet roll enters the second coagulation bath with a stretching speed of 32m/min, and then goes through the dry heat stretching of 90m/min, and then enters the shaping process, and finally produces hydroxylated alginic acid fibers.
上述方法制备得到的羟基化海藻酸纤维。The hydroxylated alginate fiber prepared by the above method.
有益效果：与现有的技术相比，本发明的优点包括：Beneficial effect: compared with the prior art, the advantages of the present invention include:
本发明通过将二价海藻酸盐粉碎的方法，物理性的减小二价海藻酸盐体积，添加到聚乙烯醇水溶液中，二价海藻酸盐与聚乙烯醇的氢键夹角小、键强度大，氢键作用力强，相容性增加；所生产纤维具有一定物理性能，单纱断裂强度≥16.5cN/dtex。The present invention physically reduces the volume of the divalent alginate by pulverizing the divalent alginate, adding it to the polyvinyl alcohol aqueous solution, the hydrogen bond angle between the divalent alginate and the polyvinyl alcohol is small, the bond High strength, strong hydrogen bond force, and increased compatibility; the produced fiber has certain physical properties, and the single yarn breaking strength is ≥16.5cN/dtex.
具体实施方式Detailed ways
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合具体实施例对本发明的具体实施方式做详细的说明。In order to make the above objects, features and advantages of the present invention more comprehensible, the specific implementation of the present invention will be described in detail below in conjunction with specific examples.
下列各实施例中，水为无离子水、纯化水或软水。检测方法参照标准和镜下试验(GB-T 14337-2008，用光学显微镜及电子显微镜方法来研究合成纤维的形态)。In each of the following examples, water is deionized water, purified water or soft water. The detection method refers to the standard and the microscopic test (GB-T 14337-2008, using optical microscopy and electron microscopy to study the morphology of synthetic fibers).
实施例1Example 1
一种羟基化海藻酸纤维的制备方法，包括以下步骤：A preparation method of hydroxylated alginic acid fiber, comprising the following steps:
第一步，凝固浴的制备The first step, the preparation of the coagulation bath
称取硫酸钠和水，硫酸钠与水的比例为35:65，形成第一凝固浴。称取氯化钙和水，氯化钙与水的比例为4:96，形成第二凝固浴。Weigh sodium sulfate and water, the ratio of sodium sulfate and water is 35:65 to form the first coagulation bath. Weigh calcium chloride and water, the ratio of calcium chloride and water is 4:96, forming the second coagulation bath.
第二步，粉碎Step two, smash
称取海藻酸钠11kg，氯化钙0.55kg，水88.45kg；将海藻酸钠加入水中，搅拌均匀后加入氯化钙，形成海藻酸钙凝胶；将含有水的海藻酸钙凝胶高速粉碎，粉碎至海藻酸钙的筛分粒度＜20μm。Weigh 11kg of sodium alginate, 0.55kg of calcium chloride, and 88.45kg of water; add sodium alginate to water, stir well and then add calcium chloride to form calcium alginate gel; crush the calcium alginate gel containing water at high speed , crushed until the sieve particle size of calcium alginate <20 μm.
第三步，纺丝原液制备The third step, spinning dope preparation
称取16kg PVA，84kg水，加热至温度高于90℃，直至聚乙烯醇完全溶解到水中，形成聚乙烯醇溶液；取上述聚乙烯醇溶液64kg，温度控制在45-55℃，加入粉碎后并带有水的海藻酸钙46kg，搅拌均匀，形成纺丝原液。Weigh 16kg of PVA and 84kg of water, heat it to a temperature higher than 90°C until the polyvinyl alcohol is completely dissolved in water to form a polyvinyl alcohol solution; take 64kg of the above polyvinyl alcohol solution, control the temperature at 45-55°C, add the pulverized And have 46kg of calcium alginate of water, stir evenly, form spinning dope.
第四步，纺丝The fourth step, spinning
纺丝原液通过计量泵，通过喷丝孔径0.08毫米，单锭吐丝量180mL/min，进入第一凝固浴，形成初生纤维，初生纤维浴中负拉伸率-19％。初生纤维随导丝辊进入第二凝固浴，延伸速度在32m/min。通过90m/min的干热延伸，再进入定型等工序，制成聚乙烯醇/海藻酸纤维。The spinning stock solution passes through the metering pump, passes through the spinneret hole diameter of 0.08 mm, and the spin rate of a single spindle is 180 mL/min, and enters the first coagulation bath to form primary fibers. The negative stretch rate in the primary fiber bath is -19%. The nascent fiber enters the second coagulation bath with the godet roller, and the extension speed is 32m/min. Through 90m/min dry heat stretching, and then enter into the shaping process to make polyvinyl alcohol/alginic acid fiber.
第五步，检测The fifth step, detection
单纱断裂强度19.7cN/tex。纤维的截面为腰圆形；有比较明显的皮芯结构，皮层与芯层 的颜色有明显的差异，且皮层较薄。横向条纹体，布满了较暗的坑点(藻酸盐)。The single yarn breaking strength is 19.7cN/tex. The cross-section of the fiber is waist-circular; there is a relatively obvious skin-core structure, the color of the cortex and the core is obviously different, and the cortex is relatively thin. Transverse striations, covered with darker pits (alginate).
实施例2Example 2
一种羟基化海藻酸纤维的制备方法，包括以下步骤：A preparation method of hydroxylated alginic acid fiber, comprising the following steps:
第一步，凝固浴的制备The first step, the preparation of the coagulation bath
称取硫酸钠和水，硫酸钠与水的比例为35:65，形成第一凝固浴。称取氯化钙和水，氯化钙与水的比例为5.5:94.5，形成第二凝固浴。Weigh sodium sulfate and water, the ratio of sodium sulfate and water is 35:65 to form the first coagulation bath. Weigh calcium chloride and water, the ratio of calcium chloride and water is 5.5:94.5 to form the second coagulation bath.
第二步，粉碎Step two, smash
称取海藻酸钠10kg，氯化钙0.5kg，水89.5kg；将海藻酸钠加入水中，搅拌均匀后加入氯化钙，形成海藻酸钙凝胶；将含有水的海藻酸钙凝胶高速粉碎，粉碎至海藻酸钙的筛分粒度＜350μm。Weigh 10kg of sodium alginate, 0.5kg of calcium chloride, and 89.5kg of water; add sodium alginate to water, stir evenly and then add calcium chloride to form calcium alginate gel; crush the calcium alginate gel containing water at high speed , crushed until the sieve particle size of calcium alginate <350 μm.
第三步，纺丝原液制备The third step, spinning dope preparation
称取16kg PVA，84kg水，加热至温度高于90℃，直至聚乙烯醇完全溶解到水中，形成聚乙烯醇溶液；取上述聚乙烯醇溶液64kg，温度控制在45-55℃，加入粉碎后并带有水的海藻酸钙46kg，搅拌均匀，形成纺丝原液。Weigh 16kg of PVA and 84kg of water, heat it to a temperature higher than 90°C until the polyvinyl alcohol is completely dissolved in water to form a polyvinyl alcohol solution; take 64kg of the above polyvinyl alcohol solution, control the temperature at 45-55°C, add the pulverized And have 46kg of calcium alginate of water, stir evenly, form spinning dope.
第四步，纺丝The fourth step, spinning
纺丝原液通过计量泵，通过喷丝孔径0.08毫米，单锭吐丝量180mL/min，进入第一凝固浴，形成初生纤维，初生纤维浴中负拉伸率-19％。初生纤维随导丝辊进入第二凝固浴，延伸速度在32m/min。通过90m/min的干热延伸，再进入定型等工序，制成聚乙烯醇/海藻酸纤维。The spinning stock solution passes through the metering pump, passes through the spinneret hole diameter of 0.08 mm, and the spin rate of a single spindle is 180 mL/min, and enters the first coagulation bath to form primary fibers. The negative stretch rate in the primary fiber bath is -19%. The nascent fiber enters the second coagulation bath with the godet roller, and the extension speed is 32m/min. Through 90m/min dry heat stretching, and then enter into the shaping process to make polyvinyl alcohol/alginic acid fiber.
第五步，检测The fifth step, detection
单纱断裂强度18.1CN/tex。纤维的截面为腰圆形；有比较明显的皮芯结构，皮层与芯层的颜色有明显的差异，且皮层较薄。横向条纹体，布满了较暗的坑点(藻酸盐)。The single yarn breaking strength is 18.1CN/tex. The cross-section of the fiber is waist-circular; there is a relatively obvious skin-core structure, the color of the cortex and the core is obviously different, and the cortex is thin. Transverse striations, covered with darker pits (alginate).
实施例3Example 3
一种羟基化海藻酸纤维的制备方法，包括以下步骤：A preparation method of hydroxylated alginic acid fiber, comprising the following steps:
第一步，凝固浴的制备The first step, the preparation of the coagulation bath
称取硫酸钠和水，硫酸钠与水的比例为35:65，形成第一凝固浴。称取氯化钙和水，氯化钙与水的比例为4:96，形成第二凝固浴。Weigh sodium sulfate and water, the ratio of sodium sulfate and water is 35:65 to form the first coagulation bath. Weigh calcium chloride and water, the ratio of calcium chloride and water is 4:96, forming the second coagulation bath.
第二步，粉碎Step two, smash
称市售海藻酸钙11kg，将海藻酸钙粉碎至的筛分粒度＜9μm。Weigh 11 kg of commercially available calcium alginate, and grind the calcium alginate to a sieve particle size of <9 μm.
第三步，纺丝原液制备The third step, spinning dope preparation
称取16kg PVA，84kg水，加热至温度高于90℃，直至聚乙烯醇完全溶解到水中，形成聚乙烯醇溶液；取上述聚乙烯醇溶液96kg，温度控制在45-55℃，加入粉碎后的海藻酸钙4kg， 搅拌均匀，形成纺丝原液。Weigh 16kg of PVA and 84kg of water, heat to a temperature higher than 90°C until the polyvinyl alcohol is completely dissolved in water to form a polyvinyl alcohol solution; take 96kg of the above polyvinyl alcohol solution, control the temperature at 45-55°C, add the pulverized 4kg of calcium alginate was mixed evenly to form a spinning dope.
第四步，纺丝The fourth step, spinning
纺丝原液通过计量泵，通过喷丝孔径0.07毫米，单锭吐丝量180mL/min，进入第一凝固浴，形成初生纤维，初生纤维浴中负拉伸率-19％。初生纤维随导丝辊进入第二凝固浴，延伸速度在32m/min。通过90m/min的干热延伸，再进入定型等工序，制成聚乙烯醇/海藻酸纤维。The spinning stock solution passes through the metering pump, passes through the spinneret hole diameter of 0.07 mm, and the spin rate of a single spindle is 180 mL/min, and enters the first coagulation bath to form primary fibers. The negative stretch rate in the primary fiber bath is -19%. The nascent fiber enters the second coagulation bath with the godet roller, and the extension speed is 32m/min. Through 90m/min dry heat stretching, and then enter into the shaping process to make polyvinyl alcohol/alginic acid fiber.
第五步，检测The fifth step, detection
单纱断裂强度16.7CN/tex。纤维的截面为腰圆形；有比较明显的皮芯结构，皮层与芯层的颜色有明显的差异，且皮层较薄。横向条纹体，布满了较暗的坑点(藻酸盐)。The single yarn breaking strength is 16.7CN/tex. The cross-section of the fiber is waist-circular; there is a relatively obvious skin-core structure, the color of the cortex and the core is obviously different, and the cortex is thin. Transverse striations, covered with darker pits (alginate).

Claims (10)

  1. 一种羟基化海藻酸纤维的制备方法，其特征在于，将二价海藻酸盐进行粉碎，粉碎后添加到聚乙烯醇水溶液中，再进行搅拌、脱泡、计量、凝固、牵伸和定型，得到羟基化海藻酸纤维。A preparation method of hydroxylated alginic acid fiber, characterized in that divalent alginate is pulverized, added to polyvinyl alcohol aqueous solution after pulverization, and then stirred, defoamed, metered, coagulated, drawn and shaped to obtain Hydroxylated alginate fibers.
  2. 根据权利要求1所述羟基化海藻酸纤维的制备方法，其特征在于，向一价海藻酸盐水溶液中添加过量的交联剂，进行暴聚反应，形成交联剂对应的二价海藻酸盐；所述交联剂为二价阳离子，为Ca 2+、Mg 2+、Ba 2+、Cu 2+、Zn 2+或Fe 2+中的任一种。 The preparation method of hydroxylated alginic acid fiber according to claim 1, characterized in that, adding an excessive amount of cross-linking agent to the monovalent alginate aqueous solution to carry out a sudden polymerization reaction to form a divalent alginate corresponding to the cross-linking agent ; The crosslinking agent is a divalent cation, which is any one of Ca 2+ , Mg 2+ , Ba 2+ , Cu 2+ , Zn 2+ or Fe 2+ .
  3. 根据权利要求1所述羟基化海藻酸纤维的制备方法，其特征在于，粉碎的二价海藻酸盐筛分粒度＜350μm。The preparation method of the hydroxylated alginate fiber according to claim 1, characterized in that the sieving particle size of the pulverized divalent alginate is less than 350 μm.
  4. 根据权利要求1所述羟基化海藻酸纤维的制备方法，其特征在于，粉碎的二价海藻酸盐筛分粒度＜20μm。The preparation method of the hydroxylated alginate fiber according to claim 1, characterized in that the sieving particle size of the pulverized divalent alginate is less than 20 μm.
  5. 根据权利要求1所述羟基化海藻酸纤维的制备方法，其特征在于，所述聚乙烯醇与二价海藻酸盐的质量比为1:99～99:1。The method for preparing hydroxylated alginate fiber according to claim 1, characterized in that the mass ratio of polyvinyl alcohol to divalent alginate is 1:99-99:1.
  6. 根据权利要求1所述羟基化海藻酸纤维的制备方法，其特征在于，所述聚乙烯醇的醇解度为70％～100％；聚乙烯醇的聚合度为450～2600。According to the preparation method of hydroxylated alginic acid fiber according to claim 1, it is characterized in that the degree of alcoholysis of the polyvinyl alcohol is 70%-100%; the degree of polymerization of the polyvinyl alcohol is 450-2600.
  7. 根据权利要求1所述羟基化海藻酸纤维的制备方法，其特征在于，所述凝固的第一凝固浴为钠盐与水的水溶液；凝固的第二凝固浴为钙盐与水的水溶液。The method for preparing hydroxylated alginate fiber according to claim 1, wherein the first coagulation bath for coagulation is an aqueous solution of sodium salt and water; the second coagulation bath for coagulation is an aqueous solution of calcium salt and water.
  8. 根据权利要求1所述羟基化海藻酸纤维的制备方法，其特征在于，先将聚乙烯醇高温溶解，温度控制在45～55℃时再添加粉碎过的二价海藻酸盐；添加二价海藻酸盐后，后续生产工艺低于60℃。According to the preparation method of hydroxylated alginate fiber according to claim 1, it is characterized in that polyvinyl alcohol is dissolved at high temperature first, and then pulverized divalent alginate is added when the temperature is controlled at 45-55°C; divalent seaweed is added After acid salt, the subsequent production process is lower than 60°C.
  9. 根据权利要求1所述羟基化海藻酸纤维的制备方法，其特征在于，具体包括以下步骤：The preparation method of hydroxylated alginic acid fiber according to claim 1, is characterized in that, specifically comprises the following steps:
    第一步，凝固浴的制备The first step, the preparation of the coagulation bath
    称取钠盐和水，制备第一凝固浴；称取钙盐和水，制备第二凝固浴；其中第一凝固浴的浓度为30～40wt.％，第二凝固浴的浓度为4～5.5wt.％；Weigh sodium salt and water to prepare the first coagulation bath; weigh calcium salt and water to prepare the second coagulation bath; wherein the concentration of the first coagulation bath is 30-40wt.%, and the concentration of the second coagulation bath is 4-5.5 wt.%;
    第二步，粉碎Step two, smash
    将一价海藻酸盐加入水中，搅拌均匀后加入交联剂，形成二价海藻酸盐凝胶；将含有水的二价海藻酸盐凝胶高速粉碎，粉碎至二价海藻酸盐的筛分粒度＜350μm；所述交联剂为二价阳离子，为Ca 2+、Mg 2+、Ba 2+、Cu 2+、Zn 2+或Fe 2+中的任一种； Add monovalent alginate into water, stir evenly and add cross-linking agent to form divalent alginate gel; crush the divalent alginate gel containing water at high speed, and crush until the sieving of divalent alginate Particle size <350 μm; the cross-linking agent is a divalent cation, any one of Ca 2+ , Mg 2+ , Ba 2+ , Cu 2+ , Zn 2+ or Fe 2+ ;
    第三步，纺丝原液制备The third step, spinning dope preparation
    将聚乙烯醇加入水中，加热至温度高于90℃，直至聚乙烯醇完全溶解到水中，形成聚乙烯醇溶液；取上述聚乙烯醇溶液，温度控制在45～55℃，加入粉碎后并带有水的二价海藻酸盐，搅拌均匀，形成纺丝原液；所述聚乙烯醇的醇解度为70％～100％；聚乙烯醇的聚合度为 450～2600；聚乙烯醇溶液的浓度为10～20wt.％；Add polyvinyl alcohol into water, heat to a temperature higher than 90°C until the polyvinyl alcohol is completely dissolved in water to form a polyvinyl alcohol solution; take the above polyvinyl alcohol solution, control the temperature at 45-55°C, add it and crush it and bring The divalent alginate with water is stirred evenly to form a spinning stock solution; the degree of alcoholysis of the polyvinyl alcohol is 70% to 100%; the degree of polymerization of the polyvinyl alcohol is 450 to 2600; the concentration of the polyvinyl alcohol solution 10-20wt.%;
    第四步，纺丝The fourth step, spinning
    纺丝原液通过计量泵，通过喷丝孔径0.07～0.08毫米，单锭吐丝量180mL/min，进入第一凝固浴，形成初生纤维，初生纤维浴中负拉伸率-19％；初生纤维随导丝辊进入第二凝固浴，延伸速度在32m/min，通过90m/min的干热延伸，再进入定型工序，最后制成羟基化海藻酸纤维。The spinning stock solution passes through the metering pump, passes through the spinneret hole diameter of 0.07-0.08 mm, and the spin rate of a single spindle is 180mL/min, and enters the first coagulation bath to form primary fibers. The negative stretch rate in the primary fiber bath is -19%; Godet roll enters the second coagulation bath, stretching speed is 32m/min, through 90m/min dry heat stretching, and then enters the shaping process, finally made into hydroxylated alginic acid fiber.
  10. 权利要求1～9所述方法制备得到的羟基化海藻酸纤维。The hydroxylated alginic acid fiber prepared by the method described in claims 1-9.
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