WO2020087503A1 - 可溶性聚电解质复合物及其对蛋白质纤维阻燃整理的方法 - Google Patents

可溶性聚电解质复合物及其对蛋白质纤维阻燃整理的方法 Download PDF

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WO2020087503A1
WO2020087503A1 PCT/CN2018/113697 CN2018113697W WO2020087503A1 WO 2020087503 A1 WO2020087503 A1 WO 2020087503A1 CN 2018113697 W CN2018113697 W CN 2018113697W WO 2020087503 A1 WO2020087503 A1 WO 2020087503A1
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flame
solution
chitosan
polyelectrolyte complex
retardant
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French (fr)
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程献伟
杨旭红
唐人成
关晋平
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Suzhou University
Nantong Textile and Silk Industrial Technology Research Institute
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Suzhou University
Nantong Textile and Silk Industrial Technology Research Institute
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    • 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
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
    • 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
    • D06M2101/10—Animal fibres
    • 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
    • D06M2101/10—Animal fibres
    • D06M2101/12—Keratin fibres or silk
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties

Definitions

  • the invention relates to a soluble polyelectrolyte complex and a method for flame retardant finishing of protein fibers, which belongs to the technical field of textile functional finishing.
  • Phytic acid is derived from plant tissues, is non-toxic, has good biocompatibility, is renewable, and has a high phosphorus content, which has attracted widespread attention in the preparation of flame-retardant polymer materials.
  • Phytic acid molecules contain phosphate groups, allowing phytic acid to combine with cationic compounds and metal ions to form complexes, so phytic acid is often used in layer-by-layer self-assembly systems to prepare intumescent flame retardant coatings.
  • Chitin the raw material of chitosan, comes from the shell of crustaceans and is widely found in nature. Natural polymer chitosan has good bio-functionality and compatibility and strong degradability, and has important applications in medicine, food, chemical and cosmetic industries.
  • chitosan can act as a blowing agent and a carbon-forming agent in the intumescent flame retardant system, and has also received extensive attention in the field of textile flame retardancy.
  • Laufer et al Alternately deposited phytic acid and chitosan on the surface of cotton fabric by layer-by-layer self-assembly to prepare an intumescent flame-retardant coating and improve the flame-retardant properties of cotton fabric, but the study required 30 cycles of coating to give Better flame retardant properties of cotton fabrics (Galina Laufer, Christopher Kirkland, Alexander B. Morgan, Jaime C. Grunlan.
  • Chinese invention patent CN103321044A discloses a flame-retardant real silk and its preparation method. The silk fabric is alternately immersed in sodium phytate and chitosan solution to prepare flame-retardant real silk through layer-by-layer assembly method, after 10 layers and above are assembled After the silk fabric obtained better flame retardant properties and washing resistance.
  • the Chinese invention patent CN105803784A discloses a method for preparing functional cotton fabrics by layer-by-layer assembly of phytic acid using polycationic polyelectrolyte polyallylamine hydrochloride.
  • the layer-by-layer assembly technology enriches polyallylamine hydrochloride and phytic acid Collected on the surface of cotton fiber, polyaniline is polymerized on the surface of cotton fiber in situ after multiple coatings, so that the cotton fabric has flame retardant properties.
  • the layer-by-layer assembly technique involves multiple impregnations of polyanion and polycation solutions, and the complicated process flow greatly limits its industrial application.
  • the object of the present invention is to provide a soluble polyelectrolyte complex and a method for flame retardant finishing of protein fibers, using natural phytic acid and chitosan as polyanion and cationic electrolyte to prepare soluble polyelectrolyte complex Flame retardant system, using citric acid as the solvent and crosslinking agent of chitosan, and applying the polyelectrolyte composite system to the flame retardant finishing of protein fibers.
  • the method has simple preparation process and short process, and the prepared flame-retardant protein fiber has excellent flame-retardant effect and good durability, and has important practical application value.
  • the first object of the present invention is to provide a method for preparing a soluble polyelectrolyte composite, including the following steps:
  • the concentration of cationic chitosan in the polyelectrolyte complex solution is 1-2%, and the concentration of citric acid is 5-7%.
  • the concentration of anionic phytic acid in the polyelectrolyte complex solution is 8-12%.
  • the pH value of the polyelectrolyte complex solution is 1-2.
  • step (1) the pH value is adjusted by adding acetic acid.
  • the citric acid is a solvent for chitosan, and serves as a cross-linking agent between chitosan and protein fibers during the flame retardant finishing process.
  • the second object of the present invention is to provide a soluble polyelectrolyte composite prepared by the method.
  • the third object of the present invention is to provide a method for flame retardant finishing of protein fibers, including the following steps:
  • step (2) Treat the protein fiber product several times according to step (1), and perform baking treatment to obtain the flame-retardant protein fiber product.
  • the protein fiber is wool and / or silk fiber.
  • step (1) the pH value of the citric acid / sodium citrate buffer solution is 4-6.
  • step (2) the number of treatment process cycles is 1-5.
  • step (2) the baking is performed at 150-160 ° C for a time of 2-4min.
  • the fourth object of the present invention is to provide a flame-retardant protein fiber product prepared by the method.
  • the principle of the present invention is: under strong acidic conditions, the degree of ionization of phosphate in phytic acid molecules is small, and there is no binding with cationic chitosan, the two are stable in solution; under weakly acidic and neutral conditions, planting
  • the phosphate ion in the acid molecule has a large degree of ionization, and can be combined with cationic chitosan by electrostatic attraction to form a complex, which is attached to the surface of the protein fiber.
  • the phytic acid / chitosan system is rich in phosphorus, nitrogen and carbon elements, and can form an intumescent flame retardant system, providing excellent flame retardant properties for protein fibers.
  • the bridging reaction between phytic acid, chitosan, citric acid and protein fiber makes the flame retardant protein fiber have better flame retardant durability, the reaction is described as follows: (1) between phytic acid and protein fiber Ionic bonding; (2) ionic bonding between phytic acid and chitosan; (3) esterification crosslinking reaction between chitosan and citric acid; (4) esterification crosslinking between citric acid and protein fiber ⁇ ⁇ Link reaction.
  • the invention uses phytic acid and chitosan to prepare a soluble polyelectrolyte composite flame retardant system under strong acidic conditions.
  • the flame retardant system has high phosphorus and nitrogen content and good flame retardant effect.
  • phytic acid and chitosan can generate ionic bonds on the surface of protein fibers and attach to the surface of protein fibers.
  • the phytic acid and chitosan flame retardant components used in the present invention are both natural products with sufficient raw material sources, and the prepared polyelectrolyte composite belongs to an environmentally friendly flame retardant system.
  • the invention has simple process, short process and low economic cost.
  • the prepared flame-retardant protein fiber has excellent flame-retardant performance, good water-washing resistance, and broad application prospects.
  • Example 2 is a graph of the heat release rate of the wool fabric in Example 4 of the present invention.
  • Example 1 Silk fabric-citric acid-one impregnation
  • chitosan (4%) is dissolved in a hydrochloric acid solution with a pH value of 1 to prepare a chitosan solution. Then, an equal volume of phytic acid (20%) solution was slowly added dropwise to the chitosan solution and stirred evenly to obtain a uniform and transparent soluble phytic acid / chitosan polyelectrolyte complex system. At this time, the concentration of phytic acid in the solution was 10%, chitosan concentration is 2%, solution pH is 1.
  • soluble polyelectrolyte complex First, dissolve chitosan (4%) in citric acid (12%) solution, and adjust the pH value of the solution to 1.3 with acetic acid to prepare chitosan solution. Then, slowly add an equal volume of phytic acid (20%) solution to the chitosan solution and mix it evenly to obtain a uniform and transparent soluble phytic acid / chitosan polyelectrolyte complex system. 10%, chitosan concentration is 2%, citric acid concentration is 6%, solution pH is 1.3.
  • the limit oxygen index (LOI) of the fabric is determined according to the standard of GB / T 5454-1997 "Oxygen Index Method for Textile Combustion Performance Test”.
  • the carbon length of the fabric is measured in accordance with the standard GB / T 5455-2014 "Determination of the length of the textile burning performance in the vertical direction of smoldering and afterburning time”.
  • the combustion performance of the fabric is evaluated according to the standard of GB / T17591-2006 "Flame Retardant Fabric".
  • the method of washing the flame retardant fabric is based on the standard GB / T 3921-2008 "Textile color fastness test soap color fastness", using silk wool detergent 2g / L, bath ratio 1:50, washing at 40 °C for 30min once. Repeat washing to the required number of times.
  • the heat release rate of the fabric was tested on an FTT0001 microcalorimeter (UK FTT company) according to ASTM D7309 (Method A).
  • Table 1 shows the LOI and carbon length of the flame-retardant silk and wool fabric after different washing times.
  • the unfinished silk and wool fabrics have LOIs of 24.8% and 23.6%, respectively, and are completely burnt during vertical combustion.
  • the carbon length is 30 cm, indicating that the untreated silk and wool fabrics have poor flame retardant properties.
  • the LOI of the silk fabric is 29.1%, and the carbon length is about 14.0 cm, indicating that the flame retardant silk fabric has good flame retardant performance.
  • the flame retardant performance of the silk fabric is further improved, and the LOI is still greater than 28.8% after 10 washings.
  • Example 3 Using hydrochloric acid as a dissolving acid agent of chitosan, the flame retardant performance of finishing silk fabrics is better, but the flame retardant performance is significantly reduced after 5 washings, and the carbon length exceeds 15.0cm after 10 washings, and cannot pass the vertical combustion test , Indicating that the flame retardant silk fabric has poor washing resistance.
  • Figures 1 and 2 show the heat release rates of the silk and wool fabrics.
  • the heat release rate of silk and wool fabrics after being treated with phytic acid / chitosan polyelectrolyte complex system is significantly reduced, indicating that the fire risk is reduced.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

本发明公开了一种可溶性聚电解质复合物及其对蛋白质纤维阻燃整理的方法，属于纺织品功能整理技术领域。本发明使用植酸和壳聚糖在强酸性条件下制备可溶性聚电解质复合物阻燃体系，再经缓冲溶液处理后植酸和壳聚糖便能在蛋白质纤维表面产生离子键结合，附着在蛋白质纤维表面。本发明中所用植酸和壳聚糖阻燃成分均为天然产物，原料来源充足，所制备的聚电解质复合物属于环境友好型阻燃体系。本发明工艺简单，流程短，经济成本低，所制备的阻燃蛋白质纤维阻燃性能优异，且耐水洗性能良好，具有广阔的应用前景。

Description

可溶性聚电解质复合物及其对蛋白质纤维阻燃整理的方法 技术领域
本发明涉及一种可溶性聚电解质复合物及其对蛋白质纤维阻燃整理的方法，属于纺织品功能整理技术领域。
背景技术
由纺织品燃烧而引起的火灾在住宅火灾事故中占有极大的比例，不仅对人类生命财产安全造成极大威胁，而且对环境造成严重污染。因此，对纺织品进行阻燃整理仍是一项重要而迫切的任务。相关研究人员开发了许多阻燃剂以改善纺织品的阻燃性能，从而降低纺织品的火灾危险性。卤素阻燃剂具有低浓高效的特点，生产效益高，被广泛应用于纺织品的阻燃整理。但卤素阻燃剂对环境和生态系统存在持久的危害，故其在纺织品上的应用受到了极大的限制。因此，绿色、无毒和可再生阻燃材料的开发引起了研究者的关注。
植酸来源于植物组织，无毒、生物相容性好、可再生，且磷元素含量较高，在制备阻燃聚合物材料方面引起了广泛关注。植酸分子中含有磷酸根基团，使得植酸能够与阳离子化合物和金属离子相结合形成复合物，故植酸常被应用于层层自组装体系以制备膨胀型阻燃涂层。壳聚糖的原料几丁质来源于甲壳类动物的外壳中，在自然界中广泛存在。天然高分子壳聚糖生物官能性和相容性好、可降解性强，在医药、食品、化工和化妆品等行业均有重要的应用。壳聚糖分子中存在含氮基团和大量羟基，故壳聚糖可充当膨胀阻燃体系中的发泡剂和成炭剂，在纺织品阻燃领域也受到了广泛的关注。Laufer等通过层层自组装的方法交替将植酸和壳聚糖沉积于棉织物表面，制备膨胀型阻燃涂层并提高棉织物的阻燃性能，但该研究需要30次循环涂层才能赋予棉织物较好的阻燃性能(Galina Laufer,Christopher Kirkland,Alexander B.Morgan,Jaime C.Grunlan. Intumescent multilayer nanocoating,made with renewable polyelectrolytes,for flame-retardant cotton.Biomacromolecules,2012,13(9):2843-2848)。中国发明专利CN103321044A公开了一种阻燃真丝绸及其制备方法，通过层层组装的方法将蚕丝织物交替浸渍于植酸钠和壳聚糖溶液中制备阻燃真丝绸，经过10层及以上组装后的真丝织物获得较好的阻燃性能和耐水洗性能。中国发明专利CN105803784A公布了一种利用阳离子聚电解质聚烯丙基胺盐酸盐层层组装植酸制备功能棉织物的方法，通过层层组装技术将聚烯丙基胺盐酸盐和植酸富集在棉纤维表面，多次涂层后将聚苯胺原位聚合在棉纤维表面，使得棉织物具有阻燃性能。但层层组装技术涉及多次浸渍聚阴离子和聚阳离子溶液，工艺流程繁杂，极大限制了其工业化应用。
发明内容
为解决上述技术问题，本发明的目的在于提供一种可溶性聚电解质复合物及其对蛋白质纤维阻燃整理的方法，以天然植酸和壳聚糖作为聚阴、阳离子电解质制备可溶性聚电解质复合物阻燃体系，使用柠檬酸作为壳聚糖的溶剂和交联剂，并将聚电解质复合物体系应用于蛋白质纤维的阻燃整理。该方法制备工艺简单，流程短，所制备的阻燃蛋白质纤维阻燃效果优异，且耐久性较好，具有重要的实际应用价值。
本发明的第一个目的是提供一种可溶性聚电解质复合物的制备方法，包括如下步骤：
(1)将壳聚糖溶解于柠檬酸溶液中，调节溶液pH值为1-2，制备得到壳聚糖溶液；
(2)将植酸溶液缓慢滴加至壳聚糖溶液中，搅拌均匀，得到均匀透明的可溶性植酸/壳聚糖聚电解质复合物溶液。
进一步地，所述聚电解质复合物溶液中阳离子壳聚糖的浓度为1-2％，柠檬酸浓度为5-7％。
进一步地，所述聚电解质复合物溶液中阴离子植酸浓度为8-12％。
进一步地，所述聚电解质复合物溶液pH值为1-2。
进一步地，在步骤(1)中，所述的pH值通过添加醋酸进行调节。
进一步地，在步骤(1)中，所述柠檬酸为壳聚糖的溶剂，且在阻燃整理过程中，充当壳聚糖和蛋白质纤维间的交联剂。
本发明的第二个目的是提供所述方法制备得到的可溶性聚电解质复合物。
本发明的第三个目的是提供蛋白质纤维阻燃整理的方法，包括如下步骤：
(1)将蛋白质纤维制品浸渍于所述的聚电解质复合物的溶液中进行整理，经烘干后，使用柠檬酸/柠檬酸钠缓冲溶液进行处理，然后水洗、烘干；
(2)按照步骤(1)对蛋白质纤维制品处理若干次，进行焙烘处理，得到所述阻燃蛋白质纤维制品。
进一步地，所述蛋白质纤维为羊毛和/或蚕丝纤维。
进一步地，在步骤(1)中，所述柠檬酸/柠檬酸钠缓冲溶液pH值为4-6。
进一步地，在步骤(2)中，所述处理工艺循环次数为1-5次。
进一步地，在步骤(2)中，所述焙烘在150-160℃下进行，时间为2-4min。
本发明的第四个目的是提供所述方法制备得到的阻燃蛋白质纤维制品。
本发明的原理是：在强酸性条件下，植酸分子中的磷酸根电离程度小，与阳离子壳聚糖不发生结合，两者在溶液中稳定存在；在弱酸性及中性条件下，植酸分子中的磷酸根电离程度大，可与阳离子壳聚糖借助静电引力结合形成复合物，附着在蛋白质纤维表面。植酸/壳聚糖体系含有丰富的磷、氮和碳元素，可组成膨胀型阻燃体系，为蛋白质纤维提供优异的阻燃性能。进一步地，植酸、壳聚糖、柠檬酸和蛋白质纤维间存在的架桥反应使得阻燃蛋白质纤维具有较好的阻燃耐久性，所述反应描述如下：(1)植酸与蛋白质纤维间的离子键结合；(2)植酸与壳聚糖间的离子键结合；(3)壳聚糖与柠檬酸间的酯化交联反应；(4)柠檬酸与蛋白质纤维间的酯化交联反应。
本发明的有益效果是：
本发明使用植酸和壳聚糖在强酸性条件下制备可溶性聚电解质复合物阻燃体系，该阻燃体系磷和氮含量高，阻燃效果好。经缓冲溶液处理后植酸和壳聚糖便能在蛋白质纤维表面产生离子键结合，附着在蛋白质纤维表面。本发明中 所用植酸和壳聚糖阻燃成分均为天然产物，原料来源充足，所制备的聚电解质复合物属于环境友好型阻燃体系。本发明工艺简单，流程短，经济成本低，所制备的阻燃蛋白质纤维阻燃性能优异，且耐水洗性能良好，具有广阔的应用前景。
附图说明
图1为本发明的实施例1和2中蚕丝织物的热释放速率图；
图2为本发明的实施例4中羊毛织物的热释放速率图。
具体实施方式
下面结合实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。
实施例1：蚕丝织物-柠檬酸-一次浸渍
(1)可溶性聚电解质复合物的制备：先将壳聚糖(2％)溶解于柠檬酸(10％)溶液中，使用醋酸调节溶液pH值为2，制得壳聚糖溶液。然后将等体积植酸(24％)溶液缓慢滴加至壳聚糖溶液中，并搅拌均匀，得到均匀透明的可溶性植酸/壳聚糖聚电解质复合物体系，此时溶液中植酸浓度为12％，壳聚糖浓度为1％，柠檬酸浓度为5％，溶液pH值为2。
(2)阻燃蚕丝织物的制备：将蚕丝织物在步骤(1)所得的聚电解质复合物溶液中浸渍10min后轧去多余水分，轧余率为100％，将蚕丝织物在70℃下烘干。然后将蚕丝织物在pH 6柠檬酸/柠檬酸钠缓冲溶液中处理5min，然后水洗、70℃下烘干，再于150℃下焙烘4min，得到阻燃蚕丝制品。
实施例2：蚕丝织物-柠檬酸-五次浸渍
(1)可溶性聚电解质复合物的制备：先将壳聚糖(4％)溶解于柠檬酸(12％)溶液中，使用醋酸调节溶液pH值为1，制得壳聚糖溶液。然后将等体积植酸(20％)溶液缓慢滴加至壳聚糖溶液中，并搅拌均匀，得到均匀透明的可溶性植酸/壳聚糖聚电解质复合物体系，此时溶液中植酸浓度为10％，壳聚糖浓度为2％，柠檬酸浓度为6％，溶液pH值为1。
(2)阻燃蚕丝织物的制备：将蚕丝织物在步骤(1)所得的聚电解质复合 物溶液中浸渍10min后轧去多余水分，轧余率为100％，将蚕丝织物在70℃下烘干。然后将蚕丝织物在pH 5柠檬酸/柠檬酸钠缓冲溶液中处理5min，然后水洗、70℃下烘干。将上述步骤重复5次，再于160℃下焙烘2min，得到阻燃蚕丝制品。
实施例3：蚕丝织物-盐酸-五次浸渍
(1)可溶性聚电解质复合物的制备：先将壳聚糖(4％)溶解于pH值为1的盐酸溶液中，制得壳聚糖溶液。然后将等体积植酸(20％)溶液缓慢滴加至壳聚糖溶液中，并搅拌均匀，得到均匀透明的可溶性植酸/壳聚糖聚电解质复合物体系，此时溶液中植酸浓度为10％，壳聚糖浓度为2％，溶液pH值为1。
(2)阻燃蚕丝织物的制备：将蚕丝织物在步骤(1)所得的聚电解质复合物溶液中浸渍10min后轧去多余水分，轧余率为100％，将蚕丝织物在70℃下烘干。然后将蚕丝织物在pH 5柠檬酸/柠檬酸钠缓冲溶液中处理5min，然后水洗、70℃下烘干。将上述步骤重复5次，再于160℃下焙烘2min，得到阻燃蚕丝制品。
实施例4：羊毛织物-柠檬酸-五次浸渍
(1)可溶性聚电解质复合物的制备：先将壳聚糖(4％)溶解于柠檬酸(12％)溶液中，使用醋酸调节溶液pH值为1.3，制得壳聚糖溶液。然后将等体积植酸(20％)溶液缓慢滴加至壳聚糖溶液中，并搅拌均匀，得到均匀透明的可溶性植酸/壳聚糖聚电解质复合物体系，此时溶液中植酸浓度为10％，壳聚糖浓度为2％，柠檬酸浓度为6％，溶液pH值为1.3。
(2)阻燃羊毛织物的制备：将羊毛织物在步骤(1)所得的聚电解质复合物溶液中浸渍10min后轧去多余水分，轧余率为100％，将羊毛织物在70℃下烘干。然后将羊毛织物在pH 4柠檬酸/柠檬酸钠缓冲溶液中处理5min，然后水洗、70℃下烘干。将上述步骤重复5次，再于160℃下焙烘2min，得到阻燃羊毛制品。
对阻燃羊毛和蚕丝织物的阻燃性能和耐水洗性能进行测试。
织物的极限氧指数(LOI)按照GB/T 5454-1997《纺织品燃烧性能实验氧 指数法》标准测定。织物的炭长按照GB/T 5455-2014《纺织品燃烧性能垂直方向损毁长度阴燃和续燃时间的测定》标准测定。织物的燃烧性能按照GB/T17591-2006《阻燃织物》标准评定。
阻燃织物的水洗方法参照GB/T 3921-2008《纺织品色牢度试验耐皂洗色牢度》标准进行，使用丝毛洗涤剂2g/L，浴比1:50，40℃下洗涤30min为一次。重复水洗至所需水洗次数。
织物的热释放速率按照ASTM D7309(方法A)在FTT0001微型量热仪(英国FTT公司)上测试。
表1所示为阻燃蚕丝和羊毛织物经不同水洗次数后的LOI和炭长。未整理蚕丝和羊毛织物的LOI分别为24.8％和23.6％，在垂直燃烧过程中均完全燃烧，炭长为30cm，表明未整理蚕丝和羊毛织物的阻燃性能差。经一次聚电解质复合物体系整理后蚕丝织物的LOI为29.1％，炭长约为14.0cm，表明阻燃蚕丝织物的阻燃性能较好。经五次聚电解质复合物体系整理后蚕丝织物的阻燃性能进一步提高，且经过10次洗涤后LOI仍大于28.8％，在垂直燃烧测试过程中能够自熄，炭长低于15.0cm，满足B 1级阻燃性能要求。根据表1所示，整理羊毛织物也具有良好的阻燃性能和耐水洗性能。实施例3使用盐酸作为壳聚糖的溶解酸剂，整理蚕丝织物的阻燃性能较好，但水洗5次后阻燃性能明显降低，水洗10次后炭长超过15.0cm，不能通过垂直燃烧测试，表明阻燃蚕丝织物的耐水洗性能较差。上述结果表明，柠檬酸的交联作用有助于提高植酸/壳聚糖聚电解复合物在蚕丝和羊毛织物上的耐水洗性能。经植酸/壳聚糖聚电解复合物整理的蚕丝和羊毛织物具有良好的阻燃性能及耐久性。
图1和图2所示为上述蚕丝和羊毛织物热释放速率图。蚕丝和羊毛织物经植酸/壳聚糖聚电解质复合物体系整理后热释放速率明显降低，表明其火灾危险性降低。
表1 阻燃蚕丝和羊毛织物经不同次数水洗后的阻燃性能
Figure PCTCN2018113697-appb-000001
以上实施案例说明用可溶性聚电解质复合物制备的蛋白中纤维制品具有优异的阻燃效果和良好的阻燃耐久性。
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例，本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换，均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。

Claims (10)

  1. 一种可溶性聚电解质复合物的制备方法，其特征在于，包括如下步骤：
    (1)将壳聚糖溶解于柠檬酸溶液中，调节溶液pH值为1-2，制备得到壳聚糖溶液；
    (2)将植酸溶液缓慢滴加至壳聚糖溶液中，搅拌均匀，得到均匀透明的可溶性植酸/壳聚糖聚电解质复合物溶液。
  2. 根据权利要求1所述的方法，其特征在于，所述聚电解质复合物溶液中壳聚糖的浓度为1-2％，柠檬酸浓度为5-7％。
  3. 根据权利要求1所述的方法，其特征在于，所述聚电解质复合物溶液中植酸浓度为8-12％。
  4. 一种权利要求1～3任一项所述的方法制备得到的可溶性聚电解质复合物。
  5. 一种利用权利要求4所述的聚电解质复合物对蛋白质纤维进行阻燃整理的方法，其特征在于，包括如下步骤：
    (1)将蛋白质纤维浸渍于聚电解质复合物的溶液中进行整理，烘干后使用柠檬酸/柠檬酸钠缓冲溶液进行处理，然后水洗、烘干；
    (2)按照步骤(1)对蛋白质纤维处理若干次，进行焙烘处理，得到所述阻燃蛋白质纤维。
  6. 根据权利要求5所述的方法，其特征在于，所述蛋白质纤维为羊毛和/或蚕丝纤维。
  7. 根据权利要求5所述的方法，其特征在于，在步骤(1)中，所述柠檬酸/柠檬酸钠缓冲溶液pH值为4-6。
  8. 根据权利要求5所述的方法，其特征在于，在步骤(2)中，对蛋白质纤维制品处理1-5次。
  9. 根据权利要求5所述的方法，其特征在于，在步骤(2)中，所述焙烘的温度为150-160℃下进行，时间为2-4min。
  10. 一种根据权利要求5所述的方法制备得到的阻燃蛋白质纤维。
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