纺织学报 ›› 2019, Vol. 40 ›› Issue (8): 181-188.doi: 10.13475/j.fzxb.20180709508

• 综合述评 • 上一篇    

聚丙烯腈纤维阻燃改性研究进展

任元林1,2(), 姜丽娜1, 霍同国1, 田甜1   

  1. 1.天津工业大学 纺织科学与工程学院, 天津 300387
    2.天津工业大学 先进纺织复合材料教育部重点实验室, 天津 300387
  • 收稿日期:2018-07-31 修回日期:2019-05-17 出版日期:2019-08-15 发布日期:2019-08-16
  • 作者简介:任元林(1971—),男,教授,博士。主要研究方向功能高分子材料。E-mail: yuanlinr@163.com。
  • 基金资助:
    国家自然科学基金面上项目(51573134)

Research progress on flame retardant modification of polyacrylonitrile fiber

REN Yuanlin1,2(), JIANG Li'na1, HUO Tongguo1, TIAN Tian1   

  1. 1. School of Textile Science and Technology, Tianjin Polytechnic University, Tianjin 300387, China
    2. Key Laboratory of Advanced Textile Composite, Ministry of Education, Tianjin Polytechnic University, Tianjin 300387, China
  • Received:2018-07-31 Revised:2019-05-17 Online:2019-08-15 Published:2019-08-16

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摘要：

为有效地解决聚丙烯腈纤维及其织物易燃的问题,推进聚丙烯腈产品的产业化应用,对国内外聚丙烯腈阻燃改性的研究进展进行综述,介绍了阻燃聚丙烯腈纤维的阻燃机制以及5种主要阻燃改性方法,并对各类方法的特点以及制备阻燃聚丙烯腈纤维存在的问题进行阐述与分析;总结了现阶段国内外阻燃聚丙烯腈的研究现状,并对未来聚丙烯腈的阻燃改性研究进行展望。指出共混法、共聚法和化学改性法有望成为产业化的主要方法;随着环保理念逐渐加强,绿色无污染无卤阻燃纤维的研究也在不断深入,无卤阻燃聚丙烯腈纤维的开发将成为研究与产业化的重心。

关键词: 无卤阻燃, 聚丙烯腈, 阻燃改性, 阻燃机制

Abstract:

In order to effectively solve the flammable defects of polyacrylonitrile fibers and its fabrics and promote the industrial application of polyacrylonitrile products, the research progress of flame retardant modification of polyacrylonitrile at home and abroad was systematically reviewed. The flame retardant mechanism and five main flame retardant modification methods of polyacrylonitrile were introduced. The characteristics and shortcomings of each method during the preparation of flame retardant polyacrylonitrile fibers were expounded and analyzed. The research status of flame retardant polyacrylonitrile at home and abroad was summarized, and the future research of flame retardant modification of polyacrylonitrile was prospected. It is pointed out that blending, copolymerization and chemical modification are expected to become the main methods of industrialization. With the concept of environmental protection gradually strengthened, the research on green environment-friendliness halogen-free flame retardant fiber is deepened, and the development of halogen-free flame retardant polyacrylonitrile fiber will become the focus of research and industrialization.

Key words: halogen-free flame retardant, polyacrylonitrile, flame retardant modification, flame retardant mechanism

中图分类号: 

  • TS102.6

表1

国外FR-PAN纤维的发展历程"

公司名称 主要产品 阻燃单体 发展历程 聚合方法
美国联合碳化物公司 维尼昂(Vinyon N)
(1950年改名为
代纳尔 Dynel)		 VC 1947年开发维尼昂(Vinyon N)纤维
1948年生产长丝产品(世界上最早的腈氯纶)
1954年长丝停产
1975年短纤停产		 水相聚合
美国伊斯曼化学公司 维勒尔(Verel) VDC 1 956开发维勒尔(Verel)
1983年停产		 水相聚合
日本钟渊化学工业株式会社 卡耐卡纶 VC 1949年生产 乳液聚合
英国考陶尔茨(Courtaulds)公司 蒂克纶 VDC 1962 年生产 水相聚合
意大利斯尼亚(SNIA)公司 韦利克纶 VDC 1965年生产
1966年推广		 溶液聚合
美国杜邦(Dupont)公司 奥纶 VDC 1973年生产 水相聚合
日本钟纺(Kinebo)株式会社 勒夫纶 VDC 1976年生产 溶液聚合
日本东丽(TORAY)株式会社 恩夫拉 VDC 1973年生产 溶液聚合
日本旭化成(Asahi KASEI)
工业株式会社		 开司米纶 VDC 1987年生产 水相聚合

表2

常用添加型阻燃剂"

化合物
类别		 化合物名称 阻燃剂的
选择条件
有机高分
子[11,18,25]		 聚氯乙烯、丙烯腈-氯乙烯共聚物、丙烯腈-偏二氯乙烯共聚物、氯乙烯-偏二氯乙烯共聚物、聚甲基膦酸酯、含烷氧基和芳氧基或氨基的聚膦嗪、聚磷酸铵、聚甲基丙烯酸甘油酯等 阻燃剂的添加量不宜过高;阻燃剂不能对纺丝原液流变性能产生影响;大分子阻燃剂的聚合度不宜过低,否则会迁移到纤维表面造成洗涤牢度下降和污染,同时会劣化纤维的性能;小分子阻燃剂要求分子质量足够大,防止阻燃物质发生迁移;阻燃剂粒度需足够细,且与体系相容性好;阻燃剂需不溶于凝固浴和水,在纺丝过程中(湿法纺丝)无堵孔的现象。
有机小分
子[11-12,24]		 四溴邻苯二酸酐、卤代磷酸酯类化合物、磷酸酯、多膦嗪、有机锡化合物、十溴二苯醚、亚烷基-双(四溴邻苯二甲酰胺)、亚烷基-双(四溴邻苯二甲酰胺)溴代芳族酰亚胺与经表面处理的纳米Sb2O3复配、Br-N-Sb高效阻燃剂、三聚氰胺、烷基磷酸酯、磷酸乙烯酯、磷酸胍等
无机小分
子[18,24-25]		 氧化锑、氯化锑、氧化钡与氧化钛的混合物、钛酸钡、草酸锌、磷酸锌、磷酸二氢铵、磷酸钙、硼酸锌、脲的复合物、乙醇锡、高岭土(DMI插层)等
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