WO2020077695A1 - Reactive flame retardant and method for durable flame retardant treatment of protein fiber using same - Google Patents

Reactive flame retardant and method for durable flame retardant treatment of protein fiber using same Download PDF

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WO2020077695A1
WO2020077695A1 PCT/CN2018/113684 CN2018113684W WO2020077695A1 WO 2020077695 A1 WO2020077695 A1 WO 2020077695A1 CN 2018113684 W CN2018113684 W CN 2018113684W WO 2020077695 A1 WO2020077695 A1 WO 2020077695A1
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flame retardant
reactive
reactive flame
protein fibers
polyol
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PCT/CN2018/113684
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French (fr)
Chinese (zh)
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唐人成
程献伟
杨旭红
关晋平
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南通纺织丝绸产业技术研究院
苏州大学
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Publication of WO2020077695A1 publication Critical patent/WO2020077695A1/en

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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
    • 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
    • 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 reactive flame retardant and a method for durable flame retardant finishing of protein fibers, which belongs to the technical field of textile functional finishing.
  • Textiles have applications in all aspects of daily life and have become an indispensable part of human life. Among them, natural protein fiber occupies an important position. However, most textiles, including protein fibers, are flammable textiles. The burning of textiles will cause serious harm to the safety of human life and property. Therefore, relevant researchers have developed many flame retardants to reduce the flammability of textiles, thereby reducing the risk of fire.
  • halogen flame retardants have been widely used in the flame retardancy of textiles and other polymer materials, but many halogen flame retardants have been proven to produce bioaccumulation and have a lasting harm to humans and animals.
  • the Zirpro flame retardant process developed by the International Wool Bureau is a relatively mature flame retardant finishing process for wool fibers. This process uses potassium hexafluorotitanate and potassium hexafluorozirconate as flame retardants. It can treat wool and silk under acidic conditions.
  • the products are processed and the wool and silk fabrics are treated with good flame retardancy, but the washing resistance is not good (Xibiao Zhang, Xian-You Zhou, Xian-Wei Cheng, Ren-Cheng Tang.Phytic Acids as eco-friendly flame-retardant for silk / wool blend: A comparative study with fluorotitanate and fluorozirconate. Journal of Cleaner Production, 2018, 198: 1044-1052).
  • Pyrovatex CP and Proban flame retardants are reactive flame retardants used for cellulose fibers, and can also be used for flame retardant finishing of protein fibers such as wool and silk.
  • Chinese patent CN201710161634.9 discloses a method for dyeing and finishing protein fibers with phytic acid.
  • the natural product phytic acid is used as both dyeing accelerator and flame retardant finishing agent. .
  • the advantage of phytic acid as a flame retardant is that it is safe and environmentally friendly, but the phytic acid molecule lacks groups that can react with the fiber, and phytic acid is easily soluble in water, so the flame retardant protein fiber treated with phytic acid alone is resistant to washing. Poor, which greatly reduces the practical application value of flame retardant protein fiber products.
  • the object of the present invention is to provide a reactive phosphorus-containing flame retardant based on phytic acid and
  • the preparation method of the flame retardant protein fiber uses natural phytic acid, polyol and polycarboxylic acid as raw materials to prepare a reactive flame retardant, and applies it to the flame retardant finishing of the protein fiber.
  • the protein fiber prepared by the method has excellent flame retardant effect, good durability and wide application prospect.
  • the first object of the present invention is to provide a method for preparing a reactive flame retardant, which includes the following steps:
  • step (1) The polyol phytate and polycarboxylic acid obtained in step (1) are subjected to an esterification reaction in a molar ratio of 1: 2 to 4 to obtain the reactive flame retardant polyol phytate carboxylate .
  • the polyol is pentaerythritol or glycerin.
  • the polycarboxylic acid described in step (2) is butane tetracarboxylic acid or citric acid.
  • step (1) the conditions of the esterification reaction are reaction at 120-130 ° C for 2 to 3 hours.
  • step (2) the conditions of the esterification reaction are reaction at 120-130 ° C for 30-45 minutes.
  • the second object of the present invention is to provide a reactive flame retardant prepared by the method.
  • the reactive flame retardant is preferably a reactive flame retardant having the molecular structure as follows:
  • the third object of the present invention is to provide a method for applying the reactive flame retardant to the durable and flame-retardant finishing of protein fibers, including the following steps:
  • step (2) Immerse the protein fibers in the flame retardant finishing liquid of step (1), and perform the second dip and second rolling treatment, and the rolling residual ratio is 90 to 110%;
  • step (3) The protein fibers treated in step (2) are prebaked and baked to obtain durable flame retardant protein fibers.
  • the protein fiber is wool and / or silk fiber.
  • the immersion time is 8-15 minutes.
  • the pre-baking and baking conditions are: drying at 60 to 90 ° C for 4 to 8 minutes, and then baking at 150 to 160 ° C for 2 to 4 minutes.
  • the fourth object of the present invention is to provide durable flame retardant protein fibers prepared by the method.
  • the phytic acid molecule contains 6 phosphate groups, which can react with the hydroxyl group of polyol such as pentaerythritol to generate polyol phytate; the residual hydroxyl group in polyol phytate and polycarboxylic acid
  • the carboxyl group in butane tetracarboxylic acid undergoes an esterification reaction to form a reactive flame retardant polyol phytate polycarboxylate.
  • the carboxyl group in the polyol phytate polycarboxylate undergoes a cross-linking reaction with the amino group and hydroxyl group in the protein fiber, so it can impart durability and flame retardant function to the protein fiber.
  • the phosphorus-containing groups in the polyol phytate polycarboxylic acid ester can promote the protein fibers to form carbon when burned, reduce the burning rate of the protein fibers, and provide excellent flame retardant properties.
  • the present invention uses phytic acid, polyol and polycarboxylic acid to prepare reactive phosphorus-containing flame retardant through esterification reaction.
  • the flame retardant has a high phosphorus content, contains multiple reactive groups in the molecule, and has high reactivity. It can be cross-linked with protein fibers during baking at high temperature without additional cross-linking agent.
  • the phytic acid used in the synthesis of the flame retardant in the present invention is a plant extract, and the resulting flame retardant is an environmentally friendly flame retardant.
  • the protein fibers finished with the flame retardant not only have excellent flame retardant properties, but also have good washing resistance, which solves the problem of poor washing resistance when using phytic acid alone to finish protein fibers.
  • Figure 1 is the infrared spectrum of phytic acid and pentaerythritol phytate butane tetracarboxylate.
  • the new absorption peaks at 1465 and 1384 cm -1 are caused by the bending vibration of the CH and CH 2 groups in the pentaerythritol and butanetetracarboxylic acid molecules.
  • the new absorption peak at 1724 cm -1 is caused by the ester bond formed between pentaerythritol and butanetetracarboxylic acid.
  • 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 vertical destruction length of the textile burning performance smoldering and afterburning time”.
  • the burning 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 detergent 2g / L, bath ratio 1:50, washing at 40 °C for 30min. once. Repeat washing to the required number of times.
  • Table 1 shows the LOI and carbon length of flame-retardant silk and wool fabrics after different washing times.
  • the unfinished wool and silk fabrics have LOIs of 23.6% and 24.8%, respectively, and are completely burned in the vertical burning process, with a carbon length of 30 cm.
  • the LOI of silk fabrics treated with 0.07mol / L reactive flame retardant is about 28.8%, and the carbon length is about 12.0cm, indicating that the flame retardant silk and wool fabrics have excellent flame retardant properties.
  • the LOI of silk and wool fabrics treated with 0.14mol / L reactive flame retardant is about 30.5%, the carbon length is about 11.5cm, and the LOI is greater than 27% after 20 washings. It can self-extinguish in the vertical combustion test. The length is still less than 15.0cm, which meets the requirements of Class B 1 flame retardant properties.
  • the above results indicate that silk and wool fabrics finished with phytic acid-based reactive flame retardants have good flame retardant properties and durability.
  • the above example shows that the fiber products in protein prepared with phytic acid-based reactive flame retardant have excellent flame retardant effect and good flame retardant durability.

Abstract

Disclosed are a reactive flame retardant and a method for the durable flame retardant treatment of protein fibers using same. In the present invention, a reactive phosphorus-containing flame retardant is prepared using phytic acid, a polyalcohol such as pentaerythritol and a polycarboxylic acid such as 1,2,3,4-butanetetracarboxylic acid by means of an esterification reaction. The flame retardant has a high phosphorus content, contains a plurality of reactive groups in molecules, has a high reaction activity, and can crosslink with protein fibers during high-temperature baking without adding an additional crosslinking agent. Phytic acid used in the synthesis of the flame retardant of the present invention is a plant extract, and the obtained flame retardant is an environmentally friendly flame retardant. The protein fibers treated with the flame retardant not only have an excellent flame retardant performance, but also have a good washing resistance, which solves the problem of the poor washing resistance when phytic acid is used alone to treat protein fibers.

Description

一种反应性阻燃剂及其对蛋白质纤维耐久阻燃整理的方法Reactive flame retardant and method for durable flame-retardant finishing of protein fiber 技术领域Technical field
本发明涉及一种反应性阻燃剂及其对蛋白质纤维耐久阻燃整理的方法，属于纺织品功能整理技术领域。The invention relates to a reactive flame retardant and a method for durable flame retardant finishing of protein fibers, which belongs to the technical field of textile functional finishing.
背景技术Background technique
纺织品在日常生活的各个方面均有应用，已经成为人类生活中不可或缺的一部分。其中天然蛋白质纤维占有重要的地位。但大部分纺织品包括蛋白质纤维属于易燃纺织品，纺织品燃烧会对人类生命财产安全造成严重的伤害。因此，相关研究人员开发了许多阻燃剂以用于降低纺织品的可燃性，从而降低火灾的危险性。Textiles have applications in all aspects of daily life and have become an indispensable part of human life. Among them, natural protein fiber occupies an important position. However, most textiles, including protein fibers, are flammable textiles. The burning of textiles will cause serious harm to the safety of human life and property. Therefore, relevant researchers have developed many flame retardants to reduce the flammability of textiles, thereby reducing the risk of fire.
随着科技的发展以及对自我保护和环境保护意识的增强，人们对生态纺织品的需求日益增加，对绿色环保型阻燃剂的开发越来越重视。卤素阻燃剂曾经被广泛应用于纺织品及其它聚合物材料的阻燃，但很多卤素阻燃剂被证实可产生生物累积，对人类和动物具有持久的危害。国际羊毛局开发的Zirpro阻燃工艺为目前应用比较成熟的羊毛纤维阻燃整理工艺，该工艺采用六氟钛酸钾和六氟锆酸钾作为阻燃剂，可在酸性条件下对羊毛和蚕丝制品进行处理，整理羊毛和蚕丝织物的阻燃性能良好，但耐水洗性能欠佳(Xibiao Zhang,Xian-You Zhou,Xian-Wei Cheng,Ren-Cheng Tang.Phytic acid as an eco-friendly flame retardant for silk/wool blend:A comparative study with fluorotitanate and fluorozirconate.Journal of Cleaner Production,2018,198:1044-1052)。另外，Pyrovatex CP和Proban阻燃剂是用于纤维素纤维的反应型阻燃剂，也可用于羊毛、蚕丝等蛋白质纤维的阻燃整理，且阻燃效果具有较好的耐久性，但用两种阻燃剂整理的织物在储存和使用过程中存在游离甲醛释放的问题。中国专利CN201710161634.9 公开了一种用植酸对蛋白质纤维进行染整加工的方法，采用天然产物植酸同时作为染色促染剂和阻燃整理剂，所处理的蛋白质纤维具有良好的阻燃性能。植酸作为阻燃剂的优点是具有安全环保性，但植酸分子中缺少可与纤维反应的基团，且植酸易溶于水，故单独用植酸处理的阻燃蛋白质纤维耐水洗性能不佳，这极大地降低了阻燃蛋白质纤维制品的实际应用价值。With the development of science and technology and the enhancement of self-protection and environmental protection awareness, people's demand for ecological textiles is increasing, and the development of green and environmentally friendly flame retardants is paying more and more attention. Halogen flame retardants have been widely used in the flame retardancy of textiles and other polymer materials, but many halogen flame retardants have been proven to produce bioaccumulation and have a lasting harm to humans and animals. The Zirpro flame retardant process developed by the International Wool Bureau is a relatively mature flame retardant finishing process for wool fibers. This process uses potassium hexafluorotitanate and potassium hexafluorozirconate as flame retardants. It can treat wool and silk under acidic conditions. The products are processed and the wool and silk fabrics are treated with good flame retardancy, but the washing resistance is not good (Xibiao Zhang, Xian-You Zhou, Xian-Wei Cheng, Ren-Cheng Tang.Phytic Acids as eco-friendly flame-retardant for silk / wool blend: A comparative study with fluorotitanate and fluorozirconate. Journal of Cleaner Production, 2018, 198: 1044-1052). In addition, Pyrovatex CP and Proban flame retardants are reactive flame retardants used for cellulose fibers, and can also be used for flame retardant finishing of protein fibers such as wool and silk. The flame retardant effect has good durability, but the two There is a problem of free formaldehyde emission during storage and use of fabrics finished with a flame retardant. Chinese patent CN201710161634.9 discloses a method for dyeing and finishing protein fibers with phytic acid. The natural product phytic acid is used as both dyeing accelerator and flame retardant finishing agent. . The advantage of phytic acid as a flame retardant is that it is safe and environmentally friendly, but the phytic acid molecule lacks groups that can react with the fiber, and phytic acid is easily soluble in water, so the flame retardant protein fiber treated with phytic acid alone is resistant to washing. Poor, which greatly reduces the practical application value of flame retardant protein fiber products.
发明内容Summary of the invention
为解决上述技术问题，为了解决现有阻燃剂应用于蛋白质纤维制品时存在的耐洗性和安全性欠佳的问题，本发明的目的是提供基于植酸的反应性含磷阻燃剂和阻燃蛋白质纤维的制备方法，以天然植酸、多元醇和多元羧酸为原料制备反应性阻燃剂，并将其应用于蛋白质纤维的阻燃整理。该方法制备的蛋白质纤维阻燃效果优异，且耐久性好，具有广泛的应用前景。In order to solve the above technical problems, in order to solve the problem that the existing flame retardants are applied to protein fiber products, the washing resistance and safety are not good, the object of the present invention is to provide a reactive phosphorus-containing flame retardant based on phytic acid and The preparation method of the flame retardant protein fiber uses natural phytic acid, polyol and polycarboxylic acid as raw materials to prepare a reactive flame retardant, and applies it to the flame retardant finishing of the protein fiber. The protein fiber prepared by the method has excellent flame retardant effect, good durability and wide application prospect.
本发明的第一个目的是提供一种反应性阻燃剂的制备方法，包括如下步骤：The first object of the present invention is to provide a method for preparing a reactive flame retardant, which includes the following steps:
(1)将植酸与多元醇按照摩尔比为1:2～4进行酯化反应，得到多元醇植酸酯；(1) Esterification reaction of phytic acid and polyol in a molar ratio of 1: 2 to 4 to obtain polyol phytate;
(2)将步骤(1)得到的多元醇植酸酯与多元羧酸按照摩尔比为1:2～4进行酯化反应，得到所述的反应性阻燃剂多元醇植酸盐羧酸酯。(2) The polyol phytate and polycarboxylic acid obtained in step (1) are subjected to an esterification reaction in a molar ratio of 1: 2 to 4 to obtain the reactive flame retardant polyol phytate carboxylate .
在本发明的一种实施方式中，在步骤(1)中，所述的多元醇为季戊四醇或丙三醇。In an embodiment of the present invention, in step (1), the polyol is pentaerythritol or glycerin.
在本发明的一种实施方式中，在步骤(2)中所述的多元羧酸为丁烷四羧酸或柠檬酸。In one embodiment of the present invention, the polycarboxylic acid described in step (2) is butane tetracarboxylic acid or citric acid.
在本发明的一种实施方式中，在步骤(1)中，所述的酯化反应的条件为在120-130℃下反应2～3h。In an embodiment of the present invention, in step (1), the conditions of the esterification reaction are reaction at 120-130 ° C for 2 to 3 hours.
在本发明的一种实施方式中，在步骤(2)中，所述的酯化反应的条件是在120-130℃下反应30～45min。In one embodiment of the present invention, in step (2), the conditions of the esterification reaction are reaction at 120-130 ° C for 30-45 minutes.
本发明的第二个目的是提供所述方法制备得到的反应性阻燃剂。The second object of the present invention is to provide a reactive flame retardant prepared by the method.
在本发明的一种实施方式中，所述的反应性阻燃剂优选为分子结构式如下的反应性阻燃剂：In one embodiment of the present invention, the reactive flame retardant is preferably a reactive flame retardant having the molecular structure as follows:
Figure PCTCN2018113684-appb-000001
Figure PCTCN2018113684-appb-000001
本发明的第三个目的是提供一种应用所述的反应性阻燃剂对蛋白质纤维耐久阻燃性整理的方法，包括如下步骤：The third object of the present invention is to provide a method for applying the reactive flame retardant to the durable and flame-retardant finishing of protein fibers, including the following steps:
(1)将所述的反应性阻燃剂溶于水中，制备得到反应性阻燃剂浓度为0.07～0.14mol/L的阻燃整理液；(1) Dissolve the reactive flame retardant in water to prepare a flame retardant finishing liquid with a concentration of reactive flame retardant of 0.07 ～ 0.14mol / L;
(2)将蛋白质纤维浸渍于步骤(1)的阻燃整理液中，进行二浸二轧处理，轧余率为90～110％；(2) Immerse the protein fibers in the flame retardant finishing liquid of step (1), and perform the second dip and second rolling treatment, and the rolling residual ratio is 90 to 110%;
(3)将步骤(2)处理后的蛋白质纤维进行预烘、烘焙处理，得到耐久阻燃蛋白质纤维。(3) The protein fibers treated in step (2) are prebaked and baked to obtain durable flame retardant protein fibers.
在本发明的一种实施方式中，所述的蛋白质纤维为羊毛和/或蚕丝纤维。In one embodiment of the present invention, the protein fiber is wool and / or silk fiber.
在本发明的一种实施方式中，在步骤(2)中，浸渍的时间为8～15min。In one embodiment of the present invention, in step (2), the immersion time is 8-15 minutes.
在本发明的一种实施方式中，在步骤(3)中，预烘、烘焙的条件为60～90℃下烘干4～8min，再于150～160℃下焙烘2～4min。In one embodiment of the present invention, in step (3), the pre-baking and baking conditions are: drying at 60 to 90 ° C for 4 to 8 minutes, and then baking at 150 to 160 ° C for 2 to 4 minutes.
本发明的第四个目的是提供所述方法制备得到的耐久阻燃蛋白质纤维。The fourth object of the present invention is to provide durable flame retardant protein fibers prepared by the method.
本发明的原理是：植酸分子中含有6个磷酸根基团，可与多元醇如季戊四醇的羟基发生酯化反应，生成多元醇植酸酯；多元醇植酸酯中残留的羟基与多元羧酸如丁烷四羧酸中的羧基发生酯化反应，生成反应性阻燃剂多元醇植酸盐多元羧酸酯。多元醇植酸盐多元羧酸酯中的羧基与蛋白质纤维中氨基和羟基发 生交联反应，因而能赋予蛋白质纤维耐久性的阻燃功能。多元醇植酸盐多元羧酸酯中的含磷基团能够促进蛋白质纤维在燃烧时成炭，降低蛋白质纤维的燃烧速率，提供优秀的阻燃性能。The principle of the present invention is: the phytic acid molecule contains 6 phosphate groups, which can react with the hydroxyl group of polyol such as pentaerythritol to generate polyol phytate; the residual hydroxyl group in polyol phytate and polycarboxylic acid For example, the carboxyl group in butane tetracarboxylic acid undergoes an esterification reaction to form a reactive flame retardant polyol phytate polycarboxylate. The carboxyl group in the polyol phytate polycarboxylate undergoes a cross-linking reaction with the amino group and hydroxyl group in the protein fiber, so it can impart durability and flame retardant function to the protein fiber. The phosphorus-containing groups in the polyol phytate polycarboxylic acid ester can promote the protein fibers to form carbon when burned, reduce the burning rate of the protein fibers, and provide excellent flame retardant properties.
本发明的有益效果是：The beneficial effects of the present invention are:
本发明通过酯化反应使用植酸、多元醇和多元羧酸制备反应性含磷阻燃剂。该阻燃剂磷含量高，分子中含有多个反应性基团，反应活性高，在高温焙烘时可与蛋白质纤维产生交联，无需额外添加交联剂。本发明中阻燃剂的合成所用的植酸是植物提取物，所得阻燃剂属于环境友好型的阻燃剂。用该阻燃剂整理的蛋白质纤维，不仅具有优异的阻燃性能，而且具有良好的耐水洗性能，解决了单独使用植酸整理蛋白质纤维时存在的耐洗性差的问题。The present invention uses phytic acid, polyol and polycarboxylic acid to prepare reactive phosphorus-containing flame retardant through esterification reaction. The flame retardant has a high phosphorus content, contains multiple reactive groups in the molecule, and has high reactivity. It can be cross-linked with protein fibers during baking at high temperature without additional cross-linking agent. The phytic acid used in the synthesis of the flame retardant in the present invention is a plant extract, and the resulting flame retardant is an environmentally friendly flame retardant. The protein fibers finished with the flame retardant not only have excellent flame retardant properties, but also have good washing resistance, which solves the problem of poor washing resistance when using phytic acid alone to finish protein fibers.
附图说明BRIEF DESCRIPTION
图1为植酸和季戊四醇植酸盐丁烷四羧酸酯的红外光谱。Figure 1 is the infrared spectrum of phytic acid and pentaerythritol phytate butane tetracarboxylate.
具体实施方式detailed description
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。The specific implementation of the present invention will be further described in detail below in conjunction with examples. The following examples are used to illustrate the present invention, but are not used to limit the scope of the present invention.
实施例1：Example 1:
(1)基于植酸的反应性阻燃剂的制备：将6.6g植酸(70％水溶液，0.007mol)和2.72g(0.02mol)季戊四醇在250mL三角烧瓶中混合均匀，于120℃下反应3h得到淡黄色粘稠液体季戊四醇植酸酯。向该混合物中加入4.68g(0.02mol)丁烷四羧酸，继续反应45min得到反应性阻燃剂季戊四醇植酸盐丁烷四羧酸酯。(1) Preparation of phytic acid-based reactive flame retardant: Mix 6.6g of phytic acid (70% aqueous solution, 0.007mol) and 2.72g (0.02mol) of pentaerythritol in a 250mL conical flask, and react at 120 ℃ for 3h Pentaerythritol phytate was obtained as a light yellow viscous liquid. To this mixture, 4.68 g (0.02 mol) of butane tetracarboxylic acid was added, and the reaction was continued for 45 minutes to obtain the reactive flame retardant pentaerythritol phytate butane tetracarboxylic acid ester.
(2)阻燃蚕丝织物的制备：将上述阻燃剂溶于100mL蒸馏水中制得阻燃剂浓度为0.07mol/L的整理液。将蚕丝织物在整理液中浸渍10min后二浸二轧，轧余率为90％，然后将蚕丝织物在60℃下烘干8min，再于150℃下焙烘4min，经水洗后干燥。(2) Preparation of flame retardant silk fabric: Dissolve the above flame retardant in 100 mL of distilled water to prepare a finishing liquid with a flame retardant concentration of 0.07 mol / L. The silk fabric was immersed in the finishing solution for 10 minutes, then dipped and rolled twice, and the rolling margin was 90%. The silk fabric was then dried at 60 ° C for 8 minutes, then baked at 150 ° C for 4 minutes, washed with water and dried.
对植酸和实施例1中制得的反应性阻燃剂季戊四醇植酸盐丁烷四羧酸酯的红外光谱进行测试，结果如图1所示。由图1可以看出，与植酸的红外光谱相比，季戊四醇植酸盐丁烷四羧酸酯红外光谱中1164和989cm -1处的吸收峰发生 明显变化，这是由季戊四醇植酸盐丁烷四羧酸酯分子中C-O基团的伸缩振动引起的。1465和1384cm -1处的新吸收峰是由季戊四醇和丁烷四羧酸分子中C-H和CH 2基团的弯曲振动引起的。另外，1724cm -1处的新吸收峰是由季戊四醇和丁烷四羧酸间形成的酯键引起的。上述结果表明成功地合成了反应性阻燃剂季戊四醇植酸盐丁烷四羧酸酯。 The infrared spectra of phytic acid and the reactive flame retardant pentaerythritol phytate butane tetracarboxylate prepared in Example 1 were tested, and the results are shown in FIG. 1. As can be seen from Figure 1, compared with the infrared spectrum of phytic acid, the absorption peaks at 1164 and 989 cm -1 in the infrared spectrum of pentaerythritol phytate butane tetracarboxylate changed significantly. It is caused by the stretching vibration of the CO group in the alkane tetracarboxylate molecule. The new absorption peaks at 1465 and 1384 cm -1 are caused by the bending vibration of the CH and CH 2 groups in the pentaerythritol and butanetetracarboxylic acid molecules. In addition, the new absorption peak at 1724 cm -1 is caused by the ester bond formed between pentaerythritol and butanetetracarboxylic acid. The above results indicate that the reactive flame retardant pentaerythritol phytate butane tetracarboxylate was successfully synthesized.
实施例2：Example 2:
(1)基于植酸的反应性阻燃剂的制备：将6.6g植酸(70％水溶液，0.007mol)和2.72g(0.02mol)季戊四醇在250mL三角烧瓶中混合均匀，于130℃下反应2h得到淡黄色粘稠液体季戊四醇植酸酯。向该混合物中加入4.68g(0.02mol)丁烷四羧酸，继续反应30min得到反应性阻燃剂季戊四醇植酸盐丁烷四羧酸酯。(1) Preparation of phytic acid-based reactive flame retardant: Mix 6.6g of phytic acid (70% aqueous solution, 0.007mol) and 2.72g (0.02mol) of pentaerythritol in a 250mL conical flask, and react at 130 ℃ for 2h Pentaerythritol phytate was obtained as a light yellow viscous liquid. 4.68 g (0.02 mol) of butane tetracarboxylic acid was added to the mixture, and the reaction was continued for 30 minutes to obtain the reactive flame retardant pentaerythritol phytate butane tetracarboxylic acid ester.
(2)阻燃蚕丝织物的制备：将上述阻燃剂溶于50mL蒸馏水中制得阻燃剂浓度为0.14mol/L的整理液。将蚕丝织物在整理液中浸渍10min后二浸二轧，轧余率为100％，然后将蚕丝织物在80℃下烘干4min，再于160℃下焙烘2min，经水洗后干燥。(2) Preparation of flame-retardant silk fabric: Dissolve the above flame retardant in 50 mL of distilled water to prepare a finishing liquid with a flame retardant concentration of 0.14 mol / L. The silk fabric was immersed in the finishing liquid for 10 minutes, then dipped and rolled twice, and the rolling margin was 100%. The silk fabric was then dried at 80 ° C for 4 minutes, then baked at 160 ° C for 2 minutes, washed with water and dried.
实施例3：Example 3:
(1)基于植酸的反应性阻燃剂的制备：将6.6g植酸(70％水溶液，0.007mol)和2.72g(0.02mol)季戊四醇在250mL三角烧瓶中混合均匀，于120℃下反应3h得到淡黄色粘稠液体季戊四醇植酸酯。向该混合物中加入4.80g(0.025mol)柠檬酸，继续反应45min得到反应性阻燃剂季戊四醇植酸盐柠檬酸酯。(1) Preparation of phytic acid-based reactive flame retardant: Mix 6.6g of phytic acid (70% aqueous solution, 0.007mol) and 2.72g (0.02mol) of pentaerythritol in a 250mL conical flask, and react at 120 ℃ for 3h Pentaerythritol phytate was obtained as a light yellow viscous liquid. To this mixture, 4.80 g (0.025 mol) of citric acid was added, and the reaction was continued for 45 minutes to obtain the reactive flame retardant pentaerythritol phytate citrate.
(2)阻燃蚕丝织物的制备：将上述阻燃剂溶于50mL蒸馏水中制得阻燃剂浓度为0.14mol/L的整理液。将蚕丝织物在整理液中浸渍10min后二浸二轧，轧余率为100％，然后将蚕丝织物在80℃下烘干5min，再于160℃下焙烘2min，经水洗后干燥。(2) Preparation of flame-retardant silk fabric: Dissolve the above flame retardant in 50 mL of distilled water to prepare a finishing liquid with a flame retardant concentration of 0.14 mol / L. The silk fabric was immersed in the finishing liquid for 10 minutes, then dipped and rolled twice, and the rolling margin was 100%. The silk fabric was then dried at 80 ° C for 5 minutes, then baked at 160 ° C for 2 minutes, washed with water and dried.
实施例4：Example 4:
(1)基于植酸的反应性阻燃剂的制备：将6.6g植酸(70％水溶液，0.007mol)和2.76g(0.03mol)丙三醇在250mL三角烧瓶中混合均匀，于130℃下反应2h得到淡黄色粘稠液体季戊四醇植酸酯。向该混合物中加入4.68g(0.02mol)丁 烷四羧酸，继续反应45min得到反应性阻燃剂丙三醇植酸盐丁烷四羧酸酯。(1) Preparation of phytic acid-based reactive flame retardant: Mix 6.6g of phytic acid (70% aqueous solution, 0.007mol) and 2.76g (0.03mol) of glycerin in a 250mL Erlenmeyer flask at 130 ℃ After 2 hours of reaction, pentaerythritol phytate was obtained as a light yellow viscous liquid. To this mixture, 4.68 g (0.02 mol) of butane tetracarboxylic acid was added, and the reaction was continued for 45 minutes to obtain the reactive flame retardant glycerol phytate butane tetracarboxylic acid ester.
(2)阻燃羊毛织物的制备：将上述阻燃剂溶于50mL蒸馏水中制得阻燃剂浓度为0.14mol/L的整理液。将羊毛织物在整理液中浸渍10min后二浸二轧，轧余率为100％，然后将羊毛织物在80℃下烘干5min，再于160℃下焙烘2min，经水洗后干燥。(2) Preparation of flame retardant wool fabric: Dissolve the above flame retardant in 50 mL of distilled water to prepare a finishing liquid with a flame retardant concentration of 0.14 mol / L. The wool fabric was immersed in the finishing liquid for 10 minutes, then dipped and rolled twice, and the rolling margin was 100%. Then the wool fabric was dried at 80 ° C for 5 minutes, then baked at 160 ° C for 2 minutes, washed with water and dried.
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。Test the flame retardant properties and washing resistance of flame retardant wool and silk fabrics.
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。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 vertical destruction length of the textile burning performance smoldering and afterburning time". The burning performance of the fabric is evaluated according to the standard of GB / T17591-2006 "Flame Retardant Fabric".
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。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 detergent 2g / L, bath ratio 1:50, washing at 40 ℃ for 30min. once. Repeat washing to the required number of times.
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。未整理羊毛和蚕丝织物的LOI分别为23.6％和24.8％，在垂直燃烧过程中均完全燃烧，炭长为30cm。经0.07mol/L反应性阻燃剂处理蚕丝织物的LOI约为28.8％，炭长约为12.0cm，表明阻燃蚕丝和羊毛织物的阻燃性能优异。经0.14mol/L反应性阻燃剂处理蚕丝和羊毛织物的LOI约为30.5％，炭长约为11.5cm，且经过20次洗涤后LOI大于27％，在垂直燃烧测试中能够自熄，炭长仍低于15.0cm，满足B 1级阻燃性能要求。上述结果表明，经基于植酸的反应性阻燃剂整理的蚕丝和羊毛织物具有良好的阻燃性能及耐久性。 Table 1 shows the LOI and carbon length of flame-retardant silk and wool fabrics after different washing times. The unfinished wool and silk fabrics have LOIs of 23.6% and 24.8%, respectively, and are completely burned in the vertical burning process, with a carbon length of 30 cm. The LOI of silk fabrics treated with 0.07mol / L reactive flame retardant is about 28.8%, and the carbon length is about 12.0cm, indicating that the flame retardant silk and wool fabrics have excellent flame retardant properties. The LOI of silk and wool fabrics treated with 0.14mol / L reactive flame retardant is about 30.5%, the carbon length is about 11.5cm, and the LOI is greater than 27% after 20 washings. It can self-extinguish in the vertical combustion test. The length is still less than 15.0cm, which meets the requirements of Class B 1 flame retardant properties. The above results indicate that silk and wool fabrics finished with phytic acid-based reactive flame retardants have good flame retardant properties and durability.
表1 阻燃蚕丝和羊毛织物经不同次数水洗后的阻燃性能Table 1 Flame retardant properties of flame-retardant silk and wool fabrics after different washing times
Figure PCTCN2018113684-appb-000002
Figure PCTCN2018113684-appb-000002
以上实施案例说明用基于植酸的反应性阻燃剂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。The above example shows that the fiber products in protein prepared with phytic acid-based reactive flame retardant have excellent flame retardant effect and good flame retardant durability.
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。The above-mentioned embodiments are only preferred embodiments for fully illustrating the present invention, and the protection scope of the present invention is not limited thereto. Equivalent substitutions or changes made by those skilled in the art on the basis of the present invention are within the protection scope of the present invention. The protection scope of the present invention is subject to the claims.

Claims (10)

  1. 一种反应性阻燃剂的制备方法，其特征在于，包括如下步骤：A method for preparing a reactive flame retardant, characterized in that it includes the following steps:
    (1)将植酸与多元醇按照摩尔比为1:2～4进行酯化反应，得到多元醇植酸酯；(1) Esterification reaction of phytic acid and polyol in a molar ratio of 1: 2 to 4 to obtain polyol phytate;
    (2)将步骤(1)得到的多元醇植酸酯与多元羧酸按照摩尔比为1:2～4进行酯化反应，得到所述的反应性阻燃剂多元醇植酸盐羧酸酯。(2) The polyol phytate and polycarboxylic acid obtained in step (1) are subjected to an esterification reaction in a molar ratio of 1: 2 to 4 to obtain the reactive flame retardant polyol phytate carboxylate .
  2. 根据权利要求1所述的反应性阻燃剂的制备方法，其特征在于，在步骤(1)中，所述的多元醇为季戊四醇或丙三醇。The method for preparing a reactive flame retardant according to claim 1, wherein in step (1), the polyol is pentaerythritol or glycerin.
  3. 根据权利要求1所述的反应性阻燃剂的制备方法，其特征在于，在步骤(2)中所述的多元羧酸为丁烷四羧酸或柠檬酸。The method for preparing a reactive flame retardant according to claim 1, wherein the polycarboxylic acid in step (2) is butane tetracarboxylic acid or citric acid.
  4. 根据权利要求1所述的反应性阻燃剂的制备方法，其特征在于，在步骤(1)中，所述的酯化反应是在120-130℃下反应2～3h。The method for preparing a reactive flame retardant according to claim 1, characterized in that, in step (1), the esterification reaction is performed at 120-130 ° C for 2 to 3 hours.
  5. 根据权利要求1所述的反应性阻燃剂的制备方法，其特征在于，在步骤(2)中，所述的酯化反应是在120-130℃下反应30～45min。The method for preparing a reactive flame retardant according to claim 1, characterized in that, in step (2), the esterification reaction is a reaction at 120-130 ° C for 30-45 minutes.
  6. 一种权利要求1～5任一项所述的方法制备得到的反应性阻燃剂。A reactive flame retardant prepared by the method of any one of claims 1 to 5.
  7. 一种应用权利要求6所述的反应性阻燃剂对蛋白质纤维耐久阻燃性整理的方法，包括如下步骤：A method for applying the reactive flame retardant of claim 6 to the durable flame retardant finishing of protein fibers includes the following steps:
    (1)将所述的反应性阻燃剂溶于水中，制备得到反应性阻燃剂浓度为0.07～0.2mol/L的阻燃整理液；(1) Dissolve the reactive flame retardant in water to prepare a flame retardant finishing liquid with a reactive flame retardant concentration of 0.07 to 0.2 mol / L;
    (2)将蛋白质纤维浸渍于步骤(1)的阻燃整理液中，进行二浸二轧处理，轧余率为90～110％；(2) Immerse the protein fibers in the flame retardant finishing liquid of step (1), and perform the second dip and second rolling treatment, and the rolling residual ratio is 90 to 110%;
    (3)将步骤(2)处理后的蛋白质纤维进行预烘、烘焙处理，得到耐久阻燃蛋白质纤维。(3) The protein fibers treated in step (2) are prebaked and baked to obtain durable flame retardant protein fibers.
  8. 根据权利要求7所述的方法，其特征在于，所述的蛋白质纤维为羊毛和/或蚕丝纤维。The method according to claim 7, wherein the protein fiber is wool and / or silk fiber.
  9. 根据权利要求7所述的方法，其特征在于，在步骤(3)中，所述的预 烘是60～90℃下烘干4～8min，所述的烘焙是在150～160℃下焙烘2～4min。The method according to claim 7, wherein in step (3), the pre-baking is drying at 60-90 ° C for 4-8 minutes, and the baking is baking at 150-160 ° C 2 ～ 4min.
  10. 一种权利要求7所述的方法制备得到的耐久阻燃蛋白质纤维。A durable flame retardant protein fiber prepared by the method of claim 7.
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