WO2019109646A1 - 一种壳聚糖-尿囊素再生纤维素纤维的制备方法 - Google Patents

一种壳聚糖-尿囊素再生纤维素纤维的制备方法 Download PDF

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WO2019109646A1
WO2019109646A1 PCT/CN2018/097858 CN2018097858W WO2019109646A1 WO 2019109646 A1 WO2019109646 A1 WO 2019109646A1 CN 2018097858 W CN2018097858 W CN 2018097858W WO 2019109646 A1 WO2019109646 A1 WO 2019109646A1
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chitosan
allantoin
solution
viscose
regenerated cellulose
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PCT/CN2018/097858
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English (en)
French (fr)
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毛军
陈红霞
陆鹏
袁红星
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江苏金太阳纺织科技股份有限公司
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Publication of WO2019109646A1 publication Critical patent/WO2019109646A1/zh

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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
    • D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
    • 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
    • D01F1/103—Agents inhibiting growth of microorganisms
    • 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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • 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
    • D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins

Definitions

  • the invention belongs to the technical field of textile raw materials, and particularly relates to a preparation method of chitosan-allantoin regenerated cellulose fibers.
  • Chitosan also known as chitin, chitosan, deacetylated chitin, soluble chitin, soluble chitin
  • Organic acids and dilute mineral acids The industrial product is a white or off-white translucent sheet-like solid with a pearly luster. It is odorless, non-toxic and easily degradable. It is a rare natural cationic polyelectrolyte.
  • Chitosan is non-toxic to the human body and does not cause secondary pollution to the environment. Therefore, it has a wide range of uses in water treatment, food, medicine and agriculture. In water treatment, it is mainly used as a polyelectrolyte coagulant, a sludge dewatering aid and a water purifying agent.
  • a flocculant when clarifying juice products, it can promote solid-liquid separation, remove acid acids and suspended solid particles from turbid juice, increase transparency, and improve product quality and grade.
  • chitosan is used as an antibacterial agent, an anticoagulant, an antiviral agent, an anticancer agent, a hemostatic agent, and a dialysis membrane.
  • it is used as a feed additive, a plant pathogen antibacterial agent, and a plant seed surface covering agent.
  • Chitosan has similar molecular structure to cellulose, and has good application properties. It is often used to prepare or modify viscose fiber with better performance. At present, there are two methods commonly used: one is to modify chitosan, such as hydroxyethylation modification, chitosan sulfonation, etc., in order to improve the compatibility between chitosan and cellulose. The fiber performance is improved; the other is to grind the chitosan into nano-sized particles and then blend with the cellulose solution to obtain the modified viscose fiber.
  • chitosan such as hydroxyethylation modification, chitosan sulfonation, etc.
  • Allantoin also known as ureidoacetic acid lactam, ureidohydantoin, urea imidazole dione, glyoxyl urea
  • Allantoin is an organic fine chemical that is soluble in hot water, hot alcohol and dilute sodium hydroxide solution. It is slightly soluble in water and alcohol at room temperature, and is insoluble in organic solvents such as ether and chloroform. It is also one of the important deep-processed products of urea, which is widely used in medicine, cosmetics and agriculture.
  • the present invention provides a method for preparing chitosan-allantoin regenerated cellulose fiber, which is a technical method for preparing a chitosan fiber due to poor dispersibility due to low solubility of chitosan.
  • the polysaccharide is dissolved in the aqueous solution of allantoin and then blended with the viscose spinning solution to prepare chitosan-allantoin regenerated cellulose fiber.
  • a method for preparing chitosan-allantoin regenerated cellulose fiber comprises the following steps:
  • Step 1 preparing a viscose spinning solution
  • Step 2 preparing a chitosan-allantoin solution: adding chitosan to an alkali solution of allantoin, dispersing;
  • step 3 the viscose spinning solution of step 1 and the solution of step 2 are blended and spun.
  • the alkali solution of the allantoin is sodium hydroxide, and the mass percentage of the alkali in the alkali solution is 5% to 10%.
  • the mass percentage of allantoin in the alkaline solution of allantoin is 5% to 10%.
  • step 2 the amount of chitosan added in step 2 is 15-20 g per 100 mL of an alkali solution of allantoin.
  • the mass ratio of the viscose spinning solution of the step 1 and the solution of the step 2 in the step 3 is 10-20:1.
  • urea may be added to the alkaline solution of allantoin in the step 2.
  • urea is added in an amount of from 1 to 3 g per 100 mL of an alkali solution of allantoin.
  • the invention dissolves chitosan in allantoin alkali solution, and utilizes the similar structure of allantoin and chitosan to greatly improve the solubility of chitosan in alkali solution and avoid the traditional chitosan adhesive.
  • the fibers directly blend the chitosan powder to obtain the disadvantage that the fibers have various properties. At the same time, it can also enhance the distribution of chitosan in the fiber, which is beneficial to enhance the antibacterial effect of the fiber and the durability of the antibacterial.
  • Allantoin is an active substance widely existed in nature. It can be industrialized and synthetically produced at present. It has the functions of repairing epithelial tissue, promoting skin ulcer and wound healing, and producing muscle. In addition, since allantoin is an amphoteric compound, it can form a double salt by combining various substances, and has the functions of protecting against light, sterilizing, antiseptic, analgesic and anti-oxidation, and keeping the skin moist, moist and soft.
  • the invention introduces allantoin into the viscose fiber, can impart fiber sterilization, anti-inflammatory, analgesic, and promote wound healing, and can also have the functions of moisturizing, softening and skin care, and greatly increasing the added value of the fiber product.
  • the raw material is a cotton pulp having a degree of polymerization of 500-600, the fiber content of which is greater than 90%, and the rubber is prepared according to the following route:
  • the viscose spinning solution has a fiber content of 8.9%, a NaOH mass fraction of 6.0, a viscosity of (falling ball method) of 59 seconds, and a ripening degree of (10% NH 4 Cl) of 8.8 mL.
  • Falling ball method The time required for a 2 mm steel ball to fall 20 cm from the viscose solution.
  • the chitosan-allantoin solution was quantitatively added to the above-mentioned viscose solution to be used by a proportional pump, and uniformly mixed.
  • the chitosan-allantoin solution was injected into the dynamic mixer at a rate of 6 liters/min using a syringe pump to mix it with the viscose solution.
  • the flow rate of the viscose solution was 50 liters/min, and it was allowed to stand at room temperature for 1 hour. .
  • the mass ratio of the viscose solution to the chitosan-allantoin solution is 10:1.
  • the mixed solution of the chitosan-allantoin solution and the viscose is sufficiently reacted and then sent to a wet spinning process for spinning.
  • the spinneret specification was 21,000 holes x 0.06 mm, the spinning speed was 55 m/min, the coagulation bath temperature was 52 ° C, and the plasticizing bath temperature was 95 ° C.
  • the composition of the coagulation bath was: 115 g/L of sulfuric acid, 325 g/L of sodium sulfate, and 11.5 g/L of zinc sulfate.
  • the raw material is a cotton pulp having a degree of polymerization of 500-600, the fiber content of which is greater than 90%, and the rubber is prepared according to the following route:
  • the viscose spinning solution has a fiber content of 8.9%, a NaOH mass fraction of 6.0, a viscosity of (falling ball method) of 59 seconds, and a ripening degree of (10% NH 4 Cl) of 8.8 mL.
  • Falling ball method The time required for a 2 mm steel ball to fall 20 cm from the viscose solution.
  • the chitosan-allantoin solution was quantitatively added to the above-mentioned viscose solution to be used by a proportional pump, and uniformly mixed.
  • the chitosan-allantoin solution was injected into the dynamic mixer at a rate of 6 liters/min using a syringe pump to mix it with the viscose solution.
  • the flow rate of the viscose solution was 50 liters/min, and it was allowed to stand at room temperature for 1 hour. .
  • the mass ratio of the viscose solution to the chitosan-allantoin solution was 15:1.
  • the mixed solution of the chitosan-allantoin solution and the viscose is sufficiently reacted and then sent to a wet spinning process for spinning.
  • the spinneret specification was 21,000 holes x 0.06 mm, the spinning speed was 55 m/min, the coagulation bath temperature was 52 ° C, and the plasticizing bath temperature was 95 ° C.
  • the composition of the coagulation bath was: 115 g/L of sulfuric acid, 325 g/L of sodium sulfate, and 11.5 g/L of zinc sulfate.
  • the raw material is a cotton pulp having a degree of polymerization of 500-600, the fiber content of which is greater than 90%, and the rubber is prepared according to the following route:
  • the viscose spinning solution has a fiber content of 8.9%, a NaOH mass fraction of 6.0, a viscosity of (falling ball method) of 59 seconds, and a ripening degree of (10% NH 4 Cl) of 8.8 mL.
  • Falling ball method The time required for a 2 mm steel ball to fall 20 cm from the viscose solution.
  • the chitosan-allantoin solution was quantitatively added to the above-mentioned viscose solution to be used by a proportional pump, and uniformly mixed.
  • the chitosan-allantoin solution was injected into the dynamic mixer at a rate of 6 liters/min using a syringe pump to mix it with the viscose solution.
  • the flow rate of the viscose solution was 50 liters/min, and it was allowed to stand at room temperature for 1 hour. .
  • the mass ratio of the viscose solution to the chitosan-allantoin solution is 20:1.
  • the mixed solution of the chitosan-allantoin solution and the viscose is sufficiently reacted and then sent to a wet spinning process for spinning.
  • the spinneret specification was 21,000 holes x 0.06 mm, the spinning speed was 55 m/min, the coagulation bath temperature was 52 ° C, and the plasticizing bath temperature was 95 ° C.
  • the composition of the coagulation bath was: 115 g/L of sulfuric acid, 325 g/L of sodium sulfate, and 11.5 g/L of zinc sulfate.
  • Example 1 The difference from Example 1 is that no chitosan-allantoin solution is added to the spinning solution.
  • the raw material is a cotton pulp having a degree of polymerization of 500-600, the fiber content of which is greater than 90%, and the rubber is prepared according to the following route:
  • the viscose spinning solution has a fiber content of 8.9%, a NaOH mass fraction of 6.0, a viscosity of (falling ball method) of 59 seconds, and a ripening degree of (10% NH 4 Cl) of 8.8 mL.
  • Falling ball method The time required for a 2 mm steel ball to fall 20 cm from the viscose solution.
  • the viscose spinning solution is sent to a wet spinning process for spinning.
  • the spinneret specification was 21,000 holes x 0.06 mm, the spinning speed was 55 m/min, the coagulation bath temperature was 52 ° C, and the plasticizing bath temperature was 95 ° C.
  • the composition of the coagulation bath was: 115 g/L of sulfuric acid, 325 g/L of sodium sulfate, and 11.5 g/L of zinc sulfate.
  • Example 1 The difference from Example 1 is that the step 2 chitosan-allantoin solution is not added with chitosan, and only allantoin is added.
  • the raw material is a cotton pulp having a degree of polymerization of 500-600, the fiber content of which is greater than 90%, and the rubber is prepared according to the following route:
  • the viscose spinning solution has a fiber content of 8.9%, a NaOH mass fraction of 6.0, a viscosity of (falling ball method) of 59 seconds, and a ripening degree of (10% NH 4 Cl) of 8.8 mL.
  • Falling ball method The time required for a 2 mm steel ball to fall 20 cm from the viscose solution.
  • the allantoin solution was quantitatively added to the above-mentioned viscose solution to be used by a proportional pump, and uniformly mixed.
  • the allantoin solution was injected into the dynamic mixer at a rate of 6 liters/min using a syringe pump, and mixed with the viscose solution uniformly.
  • the flow rate of the viscose solution was 50 liter/min, and allowed to stand at room temperature for 1 hour. Among them, the mass ratio of the viscose solution to the allantoin solution is 10:1.
  • the mixed solution of the allantoin base solution and the viscose is sufficiently reacted and then sent to a wet spinning process for spinning.
  • the spinneret specification was 21,000 holes x 0.06 mm, the spinning speed was 55 m/min, the coagulation bath temperature was 52 ° C, and the plasticizing bath temperature was 95 ° C.
  • the composition of the coagulation bath was: 115 g/L of sulfuric acid, 325 g/L of sodium sulfate, and 11.5 g/L of zinc sulfate.
  • Example 1 The difference from Example 1 was that no chitosan-allantoin solution was added to the spinning solution, and chitosan powder of the same mass as that in the chitosan-allantoin solution was added.
  • the raw material is a cotton pulp having a degree of polymerization of 500-600, the fiber content of which is greater than 90%, and the rubber is prepared according to the following route:
  • the viscose spinning solution has a fiber content of 8.9%, a NaOH mass fraction of 6.0, a viscosity of (falling ball method) of 59 seconds, and a ripening degree of (10% NH 4 Cl) of 8.8 mL.
  • Falling ball method The time required for a 2 mm steel ball to fall 20 cm from the viscose solution.
  • Allantoin (0.5%), urea (0.1%) and chitosan (1.5%) were directly added to the viscose solution, mixed, and sent to a wet spinning process for spinning.
  • the spinneret specification was 21,000 holes x 0.06 mm, the spinning speed was 55 m/min, the coagulation bath temperature was 52 ° C, and the plasticizing bath temperature was 95 ° C.
  • the composition of the coagulation bath was: 115 g/L of sulfuric acid, 325 g/L of sodium sulfate, and 11.5 g/L of zinc sulfate.
  • the fibers of the present invention were spun into yarns of the same yarn count to form a fabric of the same structure, and the bacteriostatic rate of the fabric of the example fibers was tested by the standard method of AATCC No. 6538, AATCC No. 8739, and AATCC No. 10231.
  • both molecules have an amino group (-NH 2 ) in the molecular structure, and the substance has similar compatibility characteristics, and allantoin has good solubility in an alkali solution,
  • the presence in the alkaline solution is more easily blended with the fiber spinning solution, thereby greatly improving the antibacterial and antibacterial properties of the fiber.

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Abstract

一种壳聚糖‑尿囊素再生纤维素纤维的制备方法，具体是将壳聚糖加到尿囊素的碱溶液中后再与粘胶纺丝液共混纺丝，制成再生纤维素纤维。将壳聚糖溶于尿囊素碱溶液，利用尿囊素与壳聚糖结构相似的特点能够大大提升壳聚糖在碱溶液的溶解度，避免了传统的壳聚糖的粘胶纤维直接将壳聚糖粉末共混制得纤维出现各项性能降低的缺点。同时还能提升壳聚糖在纤维中的分布，有利于提升纤维抗菌效果及抗菌的持久性。

Description

一种壳聚糖-尿囊素再生纤维素纤维的制备方法 技术领域
本发明属于纺织原料技术领域，具体涉及一种壳聚糖-尿囊素再生纤维素纤维的制备方法。
背景技术
壳聚糖(又称壳多糖、脱乙酰甲壳素、脱酰甲壳素、可溶性几丁质、可溶性甲壳素)，几乎不溶于水和碱，但溶于甲酸、乙酸、苯甲酸和环烷酸等有机酸以及稀无机酸。工业品为白色或灰白色的半透明片状固体，略带珍珠光泽。无味、无毒、易降解，是少有的天然阳离子聚电解质。以广泛存在于自然界中的低等动、植物，如节肢动物(虾、蟹)外壳中的甲壳素为原料，经加碱、加热进行脱乙酰化反应而得。壳聚糖对人体无毒，又不会对环境产生二次污染，因此，在水处理、食品、医药和农业中有广泛的用途。在水处理中，主要用作聚电解质混凝剂、污泥脱水助剂和净水剂。在食品加工中，作为絮凝剂在澄清果汁制品时，可促使固液分离，从混浊的果汁中除去果酸和悬浮固体颗粒，增加透明度，提高产品的质量和品位。在医药工业中，壳聚糖用作抗菌剂、抗凝血剂、抗病毒剂、抗癌剂、止血剂和渗析膜等。在农业中，用作饲料添加剂、植物病原体抗菌剂和植物种子表面盖覆剂等。
壳聚糖与纤维素分子结构相近，又具有较好的应用性能，多用来制备或者改性得到性能更好的粘胶纤维。目前常用的有两种方法：一是将壳聚糖改性，如羟乙基化改性、壳聚糖磺化等手段，目的是为了提升壳聚糖与纤维素之间的相容性，提升纤维性能；另一种是将壳聚糖研磨成纳米级别的颗粒后与纤维素溶液共混进行纺丝制得改性粘胶纤维。上述方法存在的缺点有：一是由于壳聚糖的溶解性能差，添加量受到限制，改性效果不佳；二是粉状的壳聚糖加入虽然不受量的限制，但是大量的粉体加入会严重影响改性纤维的机械性能。
尿囊素(又称脲基醋酸内酰胺、脲基海因、脲咪唑二酮、乙醛酰脲)，是一种有机精细化学品，能溶于热水、热醇和稀氢氧化钠溶液。微溶于常温的水和醇，难溶于乙醚和氯仿等有机溶剂，也是尿素的重要的深加工产品之一，其广泛应用于医药、化妆品、农业方面。
发明内容
解决的技术问题：本发明针对目前制备壳聚糖纤维时由于壳聚糖溶解性低导致的分散性差的技术问题，提供一种壳聚糖-尿囊素再生纤维素纤维的制备方法，将壳聚糖溶于尿囊素水 溶液后再与粘胶纺丝液共混纺丝制备得到壳聚糖-尿囊素再生纤维素纤维。
技术方案：
一种壳聚糖-尿囊素再生纤维素纤维的制备方法，包括以下步骤：
步骤1，制备粘胶纺丝液；
步骤2，配制壳聚糖-尿囊素溶液：将壳聚糖加到尿囊素的碱溶液中，分散；
步骤3，将步骤1的粘胶纺丝液和步骤2的溶液共混纺丝，即可。
进一步地，所述尿囊素的碱溶液中碱为氢氧化钠，碱溶液中碱的质量百分数为5％-10％。
进一步地，所述尿囊素的碱溶液中尿囊素的质量百分数为5％-10％。
进一步地，步骤2中壳聚糖的加入量为15-20g每100mL尿囊素的碱溶液。
进一步地，步骤3中所述步骤1的粘胶纺丝液和步骤2的溶液的质量比为10-20：1。
进一步地，步骤2中尿囊素的碱溶液中还可以加入尿素。
进一步地，尿素的加入量为1-3g每100mL尿囊素的碱溶液。
有益效果：
1.本发明将壳聚糖溶于尿囊素碱溶液，利用尿囊素与壳聚糖结构相似的特点能够大大提升壳聚糖在碱溶液的溶解度，避免了传统的壳聚糖的粘胶纤维直接将壳聚糖粉末共混制得纤维出现各项性能降低的缺点。同时还能提升壳聚糖在纤维中的分布，有利于提升纤维抗菌效果及抗菌的持久性。
2.尿囊素是自然界广泛存在的活性物质，目前已经可以工业化人工合成生产，其具有修复上皮组织，促进皮肤溃疡和伤口愈合、生肌等作用。此外，由于尿囊素是一种两性化合物，能结合多种物质形成复盐，具有避光、杀菌防腐、止痛、抗氧化作用，能使皮肤保持水份，滋润和柔软。本发明将尿囊素引入到粘胶纤维中，能够赋予纤维杀菌，消炎，止痛，促进伤口愈合等作用，还能是纤维具有滋润保湿，柔软护肤的作用，大大提升纤维制品的附加值。
具体实施方式
下面结合具体实施例对本发明的技术方案做进一步说明。
实施例1
粘胶纺丝液的制备：
原料为聚合度为500-600的棉浆粕，其甲纤含量大于90％，且按照以下工艺路线制胶：
Figure PCTCN2018097858-appb-000001
按照上述工艺制造而成粘胶纺丝液甲纤含量为8.9％，NaOH质量分数为6.0，粘度为(落球法)59s，熟程度为(10％NH 4Cl)8.8mL。
落球法：2mm钢球从所述粘胶溶液中下落20cm所需的时间。
壳聚糖-尿囊素溶液的制备：
在反应釜内，用蒸馏水配制质量分数为5％的氢氧化钠溶液，加入占氢氧化钠溶液质量5％的尿囊素和1％的尿素，充分搅拌后，再加入占氢氧化钠溶液质量15％的壳聚糖，搅拌均匀即。采用板框滤机经双层细布过滤，压力在0.2Mpa以下，得到均匀的壳聚糖-尿囊素溶液。
粘胶溶液与壳聚糖-尿囊素溶液的混合：
采用比例泵定量地将壳聚糖-尿囊素溶液加入上述待用的粘胶溶液中，并混合均匀。壳聚糖-尿囊素溶液采用注射泵以6升/min的速度注射到动态混合器中，使其与粘胶溶液混合均匀，粘胶溶液的流量为50升/min，常温下静置1h。其中，粘胶液与壳聚糖-尿囊素溶液的质量比为10:1。
湿法纺丝：
将壳聚糖-尿囊素溶液与粘胶的混合溶液充分反应后送入湿法纺丝工序进行纺丝。喷丝头规格为21000孔×0.06mm，纺丝速度为55m/min，凝固浴温度为52℃，塑化浴温度为95℃。凝固浴组成为：硫酸115g/L，硫酸钠325g/L，硫酸锌11.5g/L。
实施例2
粘胶纺丝液的制备：
原料为聚合度为500-600的棉浆粕，其甲纤含量大于90％，且按照以下工艺路线制胶：
Figure PCTCN2018097858-appb-000002
按照上述工艺制造而成粘胶纺丝液甲纤含量为8.9％，NaOH质量分数为6.0，粘度为(落球法)59s，熟程度为(10％NH 4Cl)8.8mL。
落球法：2mm钢球从所述粘胶溶液中下落20cm所需的时间。
壳聚糖-尿囊素溶液的制备：
在反应釜内，用蒸馏水配制质量分数为8％的氢氧化钠溶液，加入占氢氧化钠溶液质量8％的尿囊素和2％的尿素，充分搅拌后，再加入占氢氧化钠溶液质量18％的壳聚糖，搅拌均匀即。采用板框滤机经双层细布过滤，压力在0.2Mpa以下，得到均匀的壳聚糖-尿囊素溶液。
粘胶溶液与壳聚糖-尿囊素溶液的混合：
采用比例泵定量地将壳聚糖-尿囊素溶液加入上述待用的粘胶溶液中，并混合均匀。壳聚糖-尿囊素溶液采用注射泵以6升/min的速度注射到动态混合器中，使其与粘胶溶液混合均匀，粘胶溶液的流量为50升/min，常温下静置1h。其中，粘胶液与壳聚糖-尿囊素溶液的质量比为15:1。
湿法纺丝：
将壳聚糖-尿囊素溶液与粘胶的混合溶液充分反应后送入湿法纺丝工序进行纺丝。喷丝头规格为21000孔×0.06mm，纺丝速度为55m/min，凝固浴温度为52℃，塑化浴温度为95℃。凝固浴组成为：硫酸115g/L，硫酸钠325g/L，硫酸锌11.5g/L。
实施例3
粘胶纺丝液的制备：
原料为聚合度为500-600的棉浆粕，其甲纤含量大于90％，且按照以下工艺路线制胶：
Figure PCTCN2018097858-appb-000003
按照上述工艺制造而成粘胶纺丝液甲纤含量为8.9％，NaOH质量分数为6.0，粘度为(落球法)59s，熟程度为(10％NH 4Cl)8.8mL。
落球法：2mm钢球从所述粘胶溶液中下落20cm所需的时间。
壳聚糖-尿囊素溶液的制备：
在反应釜内，用蒸馏水配制质量分数为10％的氢氧化钠溶液，加入占氢氧化钠溶液质量10％的尿囊素和3％的尿素，充分搅拌后，再加入占氢氧化钠溶液质量20％的壳聚糖，搅拌均匀即。采用板框滤机经双层细布过滤，压力在0.2Mpa以下，得到均匀的壳聚糖-尿囊素溶液。
粘胶溶液与壳聚糖-尿囊素溶液的混合：
采用比例泵定量地将壳聚糖-尿囊素溶液加入上述待用的粘胶溶液中，并混合均匀。壳聚糖-尿囊素溶液采用注射泵以6升/min的速度注射到动态混合器中，使其与粘胶溶液混合均匀，粘胶溶液的流量为50升/min，常温下静置1h。其中，粘胶液与壳聚糖-尿囊素溶液的质量比为20:1。
湿法纺丝：
将壳聚糖-尿囊素溶液与粘胶的混合溶液充分反应后送入湿法纺丝工序进行纺丝。喷丝头规格为21000孔×0.06mm，纺丝速度为55m/min，凝固浴温度为52℃，塑化浴温度为95℃。凝固浴组成为：硫酸115g/L，硫酸钠325g/L，硫酸锌11.5g/L。
对照例1
与实施例1的区别在于：纺丝液中不加入壳聚糖-尿囊素溶液。
粘胶纺丝液的制备：
原料为聚合度为500-600的棉浆粕，其甲纤含量大于90％，且按照以下工艺路线制胶：
Figure PCTCN2018097858-appb-000004
按照上述工艺制造而成粘胶纺丝液甲纤含量为8.9％，NaOH质量分数为6.0，粘度为(落球法)59s，熟程度为(10％NH 4Cl)8.8mL。
落球法：2mm钢球从所述粘胶溶液中下落20cm所需的时间。
湿法纺丝：
将粘胶纺丝液送入湿法纺丝工序进行纺丝。喷丝头规格为21000孔×0.06mm，纺丝速度为55m/min，凝固浴温度为52℃，塑化浴温度为95℃。凝固浴组成为：硫酸115g/L，硫酸钠325g/L，硫酸锌11.5g/L。
对照例2
与实施例1的区别在于：步骤2壳聚糖-尿囊素溶液不加入壳聚糖，只加入尿囊素。
粘胶纺丝液的制备：
原料为聚合度为500-600的棉浆粕，其甲纤含量大于90％，且按照以下工艺路线制胶：
Figure PCTCN2018097858-appb-000005
按照上述工艺制造而成粘胶纺丝液甲纤含量为8.9％，NaOH质量分数为6.0，粘度为(落球法)59s，熟程度为(10％NH 4Cl)8.8mL。
落球法：2mm钢球从所述粘胶溶液中下落20cm所需的时间。
尿囊素碱溶液的制备：
在反应釜内，用蒸馏水配制质量分数为5％的氢氧化钠溶液，加入占氢氧化钠溶液质量5％的尿囊素和1％的尿素，充分搅拌后，采用板框滤机经双层细布过滤，压力在0.2Mpa以下，得到均尿囊素碱溶液。
粘胶溶液与尿囊素碱溶液的混合：
采用比例泵定量地将尿囊素碱溶液加入上述待用的粘胶溶液中，并混合均匀。尿囊素碱溶液采用注射泵以6升/min的速度注射到动态混合器中，使其与粘胶溶液混合均匀，粘胶溶液的流量为50升/min，常温下静置1h。其中，粘胶液与尿囊素碱溶液的质量比为10:1。
湿法纺丝：
将尿囊素碱溶液与粘胶的混合溶液充分反应后送入湿法纺丝工序进行纺丝。喷丝头规格为21000孔×0.06mm，纺丝速度为55m/min，凝固浴温度为52℃，塑化浴温度为95℃。凝固浴组成为：硫酸115g/L，硫酸钠325g/L，硫酸锌11.5g/L。
对照例3
与实施例1的区别在于：纺丝液中不加入壳聚糖-尿囊素溶液，加入与壳聚糖-尿囊素溶液中相同质量的壳聚糖粉末。
粘胶纺丝液的制备：
原料为聚合度为500-600的棉浆粕，其甲纤含量大于90％，且按照以下工艺路线制胶：
Figure PCTCN2018097858-appb-000006
按照上述工艺制造而成粘胶纺丝液甲纤含量为8.9％，NaOH质量分数为6.0，粘度为(落球法)59s，熟程度为(10％NH 4Cl)8.8mL。
落球法：2mm钢球从所述粘胶溶液中下落20cm所需的时间。
湿法纺丝：
将尿囊素(0.5％)、尿素(0.1％)和壳聚糖(1.5％)直接加至粘胶液中，混合后送入湿法纺丝工序进行纺丝。喷丝头规格为21000孔×0.06mm，纺丝速度为55m/min，凝固浴温度为52℃，塑化浴温度为95℃。凝固浴组成为：硫酸115g/L，硫酸钠325g/L，硫酸锌11.5g/L。
纤维的断裂强度、断裂伸长和变异系数测试依据“GB/T 14337-2008化学纤维短纤维拉伸性能试验方法”执行。
将本发明的纤维纺成同一纱支的纱线后织造成相同组织的面料，采用AATCC NO.6538、AATCC NO.8739、AATCC NO.10231标准方法测试实施例纤维制成面料的抑菌率。
Figure PCTCN2018097858-appb-000007
从上表的测试结果可以看出：由于壳聚糖与尿囊素两种物质具有一定的抗菌抑菌性能，因此将壳聚糖和尿囊素加入到再生纤维素纤维中能够提升纤维的抗菌抑菌性能，尤其是二者同时加入的情况下。当纺丝液中只加入壳聚糖时，由于壳聚糖在碱溶液中的溶解度较低，影响了壳聚糖的加入量，最终导致纤维的抗菌抑菌性能欠佳。同样，如果在纺丝液中仅仅加入尿囊素，尿囊素的抗菌抑菌效果较弱，纤维也无法具有较好的抗菌性能。而将二者同时加入时，由于二者分子结构中都具有氨基(-NH 2)，且物质具有相似相容的特点，同时尿囊素在碱溶液中具有较好的溶解性能，因此促进二者在碱溶液中的存在，更容易与纤维纺丝液共混，从而能够大幅提升纤维的抗菌抑菌性能。

Claims (7)

  1. 一种壳聚糖-尿囊素再生纤维素纤维的制备方法，其特征在于：包括以下步骤：
    步骤1，制备粘胶纺丝液；
    步骤2，配制壳聚糖-尿囊素溶液：将壳聚糖加到尿囊素的碱溶液中，分散；
    步骤3，将步骤1的粘胶纺丝液和步骤2的溶液粘胶纺丝液，即可。
  2. 根据权利要求1所述的壳聚糖-尿囊素再生纤维素纤维的制备方法，其特征在于：所述尿囊素的碱溶液中碱为氢氧化钠，碱溶液中碱的质量百分数为5％-10％。
  3. 根据权利要求2所述的壳聚糖-尿囊素再生纤维素纤维的制备方法，其特征在于：所述尿囊素的碱溶液中尿囊素的质量百分数为5％-10％。
  4. 根据权利要求1所述的壳聚糖-尿囊素再生纤维素纤维的制备方法，其特征在于：步骤2中壳聚糖的加入量为15-20g每100mL尿囊素的碱溶液。
  5. 根据权利要求1所述的壳聚糖-尿囊素再生纤维素纤维的制备方法，其特征在于：步骤3中所述步骤1的粘胶纺丝液和步骤2的溶液的质量比为10-20：1。
  6. 根据权利要求1所述的壳聚糖-尿囊素再生纤维素纤维的制备方法，其特征在于：步骤2中尿囊素的碱溶液中还可以加入尿素。
  7. 根据权利要求6所述的壳聚糖-尿囊素再生纤维素纤维的制备方法，其特征在于：尿素的加入量为1-3g每100mL尿囊素的碱溶液。
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