聚丙烯腈无卤阻燃及其抑烟技术研究进展

doi:10.13475/j.fzxb.20180709607

摘要/Abstract

摘要：

为推进聚丙烯腈无卤阻燃技术的进一步发展,同时为聚丙烯腈无卤阻燃技术的科学研究与产业化应用提供参考,阐述了聚丙烯腈纤维及其织物的主要阻燃技术,常用无卤阻燃剂的类别及不同无卤阻燃剂的主要抑烟机制。综述了国内外聚丙烯腈无卤阻燃及抑烟技术的发展概况和最新研究进展。针对不同无卤阻燃剂的缺点提出了对应的解决方案和发展要求。分析了国内外聚丙烯腈无卤阻燃技术的发展差异,并提出了相应建议。展望了未来聚丙烯腈阻燃技术的发展,指出高效、抑烟、环保的阻燃整理技术将会成为未来阻燃聚丙烯腈研究领域的重要发展方向。

关键词: 聚丙烯腈, 无卤阻燃, 阻燃整理, 阻燃剂, 抑烟

Abstract:

In order to promote the further development of halogen-free flame retardant technology of polyacrylonitrile and provide reference for the scientific research and industrial application, the main flame retardant technologies suitable for polyacrylonitrile fiber and its fabric, the types of the commonly used halogen-free flame retardants and the main smoke suppression mechanisms of different halogen-free flame retardants were introduced. The development and the latest research progress of halogen-free flame retardants and their smoke suppression technology of polyacrylonitrile at home and abroad were reviewed. As far as the shortcomings of the different halogen-free flame retardants were concerned, corresponding solutions and development requirements were put forward. The different developments of halogen-free flame retardant of polyacrylonitrile at home and abroad were analyzed and the corresponding suggestions were put forward. It presents a new prospect for the development of flame retardant technology for polyacrylonitrile in the future. In addition, it points out that high efficiency, smoke suppression and environmental-friendly flame retardant technology will become an important development direction of flame retardant polyacrylonitrile in the future.

Key words: polyacrylonitrile, halogen-free flame retardant, flame retandant finishing, flame retardant agent, smoke suppression

中图分类号:

TS102.5

任元林, 姜丽娜, 霍同国, 田甜. 聚丙烯腈无卤阻燃及其抑烟技术研究进展[J]. 纺织学报, 2019, 40(07): 182-188.

REN Yuanlin, JIANG Li'na, HUO Tongguo, TIAN Tian. Research progress of halogen-free flame retardancy and smoke suppression of polyacrylonitrile[J]. Journal of Textile Research, 2019, 40(07): 182-188.

图/表 1

表1

参考文献 45

[1]	任元林, 张悦, 谷叶童 , 等. 含磷阻燃聚丙烯腈纤维的制备及其性能[J]. 纺织学报, 2017,38(8):1-5.
	REN Yuanlin, ZHANG Yue, GU Yetong , et al. Preparation and properties of phosphorus containing flame retardant polyacrylonitrile fibers[J]. Journal of Textile Research, 2017,38(8):1-5.
[2]	任元林, 张悦, 曾倩 , 等. 织物阻燃涂层新工艺的研究进展[J]. 纺织学报, 2017,38(9):168-173.
	REN Yuanlin, ZHANG Yue, ZENG Qian , et al. Research progress of new flame retardant coating technology for fabrics[J]. Journal of Textile Research, 2017,38(9):168-173.
[3]	LI Z, CHENG X D, GONG L L , et al. Enhanced flame retardancy of hydrophobic silica aerogels by using sodium silicate as precursor and phosphoric acid as catalyst[J]. Journal of Non-Crystalline Solids, 2018,481:267-275.
[4]	MICHALL E, HALL A, HORROCS R , et al. The flammability of polyacryionitrile and its copolymers[J]. Polymer Degradation and Stability, 1994,44:379-386.
[5]	JOSEPH P, TRETSIAKOVA-MCNALLY S . Combustion behaviours of chemically modified polyacrylonitrile polymers containing phosphory-lamino groups[J]. Polymer Degradation and Stability, 2012,97:2531-2535.
[6]	BALLISTRE A, MONTAUDOG, PUGLISI C , et al. Intumescentflame retardants for polymers: I: the poly(acrylonitrile)-ammonium polyphosphate hex- abromocyclododecane system[J]. Journal of Applied polymers Science, 1983,28(5):1743-1750.
[7]	方军, 邬国铭, 梅千芳 , 等. NaSCN溶剂法纺制非卤系阻燃腈纶的研究[J]. 华南理工大学学报(自然科学版), 1996,24(7):121-127.
	FANG Jun, WU Guoming, MEI Qianfang , et al. Study on NaSCN solvent spinning of non-halogen flame retardant acrylic fiber[J]. Journal of South China University of Technology(Natural Science Edition), 1996,24(7):121-127.
[8]	王永强 . 阻燃材料及应用技术[M]. 北京: 化学工业出版社, 2003: 457-467.
	WANG Yongqiang. Flame Retardant Materials and Application Technology [M]. Beijing: Chemical Industry Press, 2003: 457-467.
[9]	徐建中 . 纤维(聚丙烯腈纤维、麻、羊毛)和软 PVC塑料热降解及阻燃机理的研究[D]. 保定:河北大学, 2003: 4-32.
	XU Jianzhong . Study on thermal degradation and flame retardant mechanism of fiber (polyacry lonitrile fiber, hemp, wool) and soft PVC plastic[D]. Baoding: Hebei University, 2003: 4-32.
[10]	赵择卿, 陆大年, 马艳玲 , 等. 聚丙烯腈阻燃改性纤维的研究[J]. 纺织学报, 1988,9(1):5-10.
	ZHAO Zeqing, LU Danian, MA Yanling , et al. Study on polyacrylonitrile flame retardant modified fiber[J]. Journal of Textile Research, 1988,9(1):5-10.
[11]	汪津 . 无卤阻燃剂的研究进展[J]. 印染, 2017,43(8):56-57.
	WANG Jin . Research progress of halogen-free flame retardants[J]. China Dyeing & Finishing, 2017,43(8):56-57.
[12]	SANTANU B, ALI S W . Sustainable fire retardancy of textile using biomacromolecules[J]. Polymer Degradation and Stability, 2016,133.
[13]	LIU H C, CHIEN A T, NEWCOMB A B , et al. Stabilization kinetics of gel spun polyacrylonitrile /lignin blend fiber[J]. Carbon, 2016,101:382-389.
[14]	邹志量 . 腈纶无卤阻燃状况[C]// 杨荣杰,孙玉泉,周正懋,等. 2010年中国阻燃学术会议论文集. 北京:中国阻燃学会, 2010: 6.
	ZOU Zhiliang . Halogen-free flame retardant status of acrylic fibers[C]// YANG Rongjie, SUN Yuquan, ZHOU Zhengmao, et al. Proceedings of China Flame Retardant Conference 2010. Beijing: China Flame Retardant Society, 2010: 6.
[15]	WYMAN P, CROOK V, EBDON J , et al. Flameretarding effects of dialkyl-p-vinylbenzyl phosphonates in copolymers with acrylonitrile[J]. Polymer International, 2006,55:764-771.
[16]	TSAFACKM J, LEVALOIS-GRUTZMACHER J . Plasma-induced graft-polymerization of flame retardant monomers onto PAN fabrics[J]. Surface and Coatings Technology, 2006,200(11):3503-3510.
[17]	CROOK V, EBON J, HUNT B , et al. The influence of comonomers on the degradation and flamability of polyacrylonitrile: design input for a new generation of flame retardants[J]. Polymer Degradation and Stability, 2010,95(12):2260-2268.
[18]	BAJAJ P, SREEKUMAR T V, SEN K . Thermal behavior of acrylonitrile copolymers having methacrylic and itaconic acid comonomers[J]. Polymer, 2001,42(4):1707-1718.
[19]	GUYOT A, BERT M, HAMOUD A , et al. Pyrolysis of acrylonitrile-methacrylic acid copolymers and deriva-tives[J]. European Polymer, 1978,14:101-107.
[20]	JI L W, CARLS , SAAD A K, et al. Preparation and characterization of silica nano-particulate polyacrylonitrile composite and porousnano-fibers[J]. Nano-technology, 2008,19:085605.
[21]	TAHIRA P, SARA A, CARL D S , et al. Hybrid carbon silica nanofibers through sol-gel electro-spinning[J]. Langmuir, 2014,30:15504-15513. doi: 10.1021/la503290n pmid: 25474752
[22]	MOONS C, EMRICK T . High flame resistant and strong electrospun polyacrylonitrile-carbon nanotubes-ochre nanofibers[J]. Polymer, 2013,54(7):1813-1819.
[23]	ALMUHAMED S, BONNE M, KHENOUSSI N , et al. Electrospinning composite nanofibers of polyacrylonitrile/synthetic Na-montmorillonite[J]. Journal of Industrial and Engineering Chemistry, 2016,35:146-152. doi: 10.1016/j.jiec.2015.12.024
[24]	MADAKBA S E, ÇAKMAKM V . Preparation and thermal properties of polyacry lonitrile/hexagonal boron nitride composites[J]. Thermochimica Acta, 2013,552:1-4. doi: 10.1016/j.tca.2012.11.011
[25]	常承飞 . 聚丙烯腈基阻燃纤维的研究[D]. 上海:东华大学, 2017: 10-34.
	CHANG Chengfei . Study on polyacrylonitrile-based flame retardant fiber[D]. Shanghai: Donghua University, 2017: 10-34.
[26]	曹机良, 孟春丽, 李晓春 , 等. 一种阻燃腈纶的制备方法:201610239504.8[P]. 2016-04-18.
	CAO Jiliang, MENG Chunli, LI Xiaochun , et al. Preparation of a flame retardant acrylic fiber: China: 201610239504.8[P]. 2016-04-18.
[27]	邹志量 . 无卤阻燃改性聚丙烯腈的合成及其性能的研究[C]// 周其凤,董建华,李杨,等. 2011年全国高分子学术论文报告会论文摘要集. 北京:中国化学会高分子学科委员会, 2011: 1.
	ZOU Zhiliang . Study on synconfproc and properties of halogen-free flame retardant modified polyacryloni-trile[C]// ZHOU Qifeng, DONG Jianhua, LI Yang, et al.Abstract Summary of the 2011 National Polymer Academic Papers Conference.Beijing: Polymer Subject Committee of Chinese Chemical Society, 2011: 1.
[28]	刘艳春, 何珠仪, 白刚 , 等. 腈纶织物的氰基水解酶/硼酸锌阻燃整理[J]. 纺织学报, 2016,37(3):110-113.
	LIU Yanchun, HE Zhuyi, BAI Gang , et al. Flame retardant finishing of cyanohydrolase/zinc borate for acrylic fabrics[J]. Journal of Textile Research, 2016,37(3):110-113.
[29]	赵斯梅 . 无卤阻燃聚丙烯腈的合成及性能分析[J]. 山东纺织经济, 2012(4):49-51.
	ZHAO Simei . Synjournal and performance analysis of halogen-free flame retardant polyacrylonitrile[J]. Shandong Textile Economy, 2012(4):49-51.
[30]	朱军 . 腈纶预环化预氧化制备阻燃纤维研究[D]. 淄博:山东理工大学, 2010: 12-48.
	ZHU Jun . Study on preparation of flame retardant fiber by preoxidation of acrylic fiber[D]. Zibo: Shandong University of Technology, 2010, 12-48.
[31]	李国昌, 杨彦功, 贾曌 , 等. PAN与硫氰酸根插层水滑石共混体系初探[J]. 纺织学报, 2007,28(5):28-31.
	LI Guochang, YANG Yangong, JIA Wei , et al. Preliminary study on blending system of PAN and thiocyanate intercalated hydrotalcite[J]. Journal of Textile Research, 2007,28(5):28-31.
[32]	贾曌, 杨彦功 . 高岭石/聚丙烯腈插层共混体系的结构及性能[J]. 高分子材料科学与工程, 2008,24(2):111-114.
	JIA Wei, YANG Yangong . Structure and properties of kaolinite/polyacrylonitrile intercalation blend system[J]. Journal of Polymer Materials Science and Engineering, 2008,24(2):111-114.
[33]	李佳齐 . 聚丙烯腈与改性酶解木质素共混纤维的制备与性能[J]. 材料科学与工程学报, 2018(2):218-222.
	LI Jiaqi . Preparation and properties of polyacrylonitrile and modified enzymatic lignin blend fibers[J]. Journal of Materials Science and Engineering, 2018(2):218-222
[34]	贾曌, 杨彦功 . 水滑石在阻燃聚丙烯腈纤维改性中的应用研究[J]. 合成纤维, 2009,38(5):8-10.
	JIA Wei, YANG Yangong . Application of hydrotalcite in the modification of flame retardant polyacrylonitrile fiber[J]. Synthetic Fiber, 2009,38(5):8-10
[35]	刘群, 丁斌, 关昶 , 等. 腈纶的磷氮系膨胀型阻燃整理研究[J]. 毛纺科技, 2016,44(12):31-33.
	LIU Qun, DING Bin, GUAN Wei , et al. Study on phosphorus and nitrogen intumescent flame retardant finishing of acrylic fiber[J]. Wool Textile Journal, 2016,44(12):31-33.
[36]	任元林, 王灵杰, 刘甜甜 . 无卤阻燃聚丙烯腈纤维的制备及性能[J]. 高分子材料科学与工程, 2016,32(5):130-133.
	REN Yuanlin, WANG Lingjie, LIU Tiantian . Preparation and properties of halogen-free flame retardant polyacrylonitrile fiber[J]. Polymer Materials Science and Engineering, 2016,32(5):130-133.
[37]	任元林, 霍同国, 秦一文 , 等. 聚丙烯腈/聚乙烯醇无卤阻燃纤维的性能研究[J]. 纺织科学与工程学报, 2018,35(2):82-85.
	REN Yuanlin, HUO Tongguo, QIN Yiwen , et al. Study on properties of polyacrylonitrile/polyvinyl alcohol halogen-free flame retardant fiber[J]. Journal of Textile Science and Engineering, 2018,35(2):82-85.
[38]	REN Yuanlin, ZHANG Yue, GU Yetong , et al. Flame retardant polyacrylonitrile fabrics prepared by organic- inorganic hybrid silica coating via sol-gel technique[J]. Progress in Organic Coatings, 2017,112:225-233.
[39]	REN Yuanlin, HUO Tongguo, QIN Yiwen , et al. Preparation of flame retardant polyacrylonitrile fabric based on sol-gel and layer-by-layer assembly[J]. Material, 2018(11):483.
[40]	REN Yuanlin, GU Yetong . UV-induced surface grafting polymerizationfor preparing phosphorus-containing flame retardant polyacrylonitrile fabric[J]. European Polymer Journal, 2017,94:1-10.
[41]	ZHANG Yue, REN Yuanlin, LIU Xiaohui , et al. Preparation of durable flame retardant PAN fabrics based on amid oximation and phosphorylation[J]. Applied Surface Science, 2018,428:395-403.
[42]	REN Yuanlin, JIANG Lina, TIAN Tian , et al. Durable flame retardant polyacrylonitrile fabric via UV-induced grafting polymerization and surface chemical modifi-cation[J]. RSC Advances, 2018(8):41389-41396.
[43]	周地平 . 阻燃腈纶的技术现状及市场分析[J]. 石油化工技术与经济, 2017,33(6):16-19.
	ZHOU Diping . Technical status and market analysis of flame retardant acrylic fiber[J]. Petrochemical Technology and Economy, 2017,33(6):16-19.
[44]	徐玲, 程博闻, 任元林 , 等. 阻燃聚丙烯腈及其纤维的研究进展[J]. 纺织学报, 2010,31(8):146-150.
	XU Ling, CHENG Bowen, REN Yuanlin , et al. Research progress of flame retardant polyacry lonitrile and its fibers[J]. Journal of Textile Research, 2010,31(8):146-150.
[45]	BASAK S, ALI S W . Sustainable fire retardancy of textiles using biomacromolecule[J]. Polymer Degradation and Stability, 2016,133:47-64.

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阻燃方法	主要工艺	优点	缺点
共混	将阻燃剂添加到纺丝液中	工艺简单易行,成本低,产品耐水洗性较好	对阻燃剂的粒径与纺丝液的相容性要求都很高。阻燃剂选择困难
共聚	将含阻燃元素的不饱和化合物与丙烯腈共聚,进而纺丝得到阻燃聚丙烯腈纤维	阻燃耐久性较好、对纤维和织物的力学性能影响不大,可纺性高	共聚单体的选择困难、生产成本较高、工艺较复杂
热氧化	将聚丙烯腈原丝置于200~300 ℃的空气氧化炉里,在一定张力下氧化一定时间	阻燃纤维强度保持率高、LOI值可高达55%~62%,阻燃性能优良	对聚丙烯腈原丝要求很高
接枝共聚	通过热、氧、光等的作用在PAN纤维或织物表面接枝上阻燃元素或基团	成本低,工艺绿色环保,对织物力学性能影响小	聚合物自由基利用率较低
后整理	浸渍涂层、溶胶-凝胶、层层自组装、生物大分子沉积	生产工艺简单,易于操作,成本较低	耐水洗性差, 影响织物手感
复合纺丝法	以阻燃高聚物为皮层、聚丙烯腈为芯层进行复合纺丝	纤维具有良好的力学性能、均匀性和稳定性	工艺较复杂,对设备技术要求高