Journal of Textile Research ›› 2019, Vol. 40 ›› Issue (8): 181-188.doi: 10.13475/j.fzxb.20180709508

• Comprehensive Review • Previous Articles    

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

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

CLC Number: 

  • TS102.6

Tab.1

Development of foreign flame retardant polyacrylonitrile fiber"

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

Tab.2

Commonly used additive flame retardants"

化合物
类别
化合物名称 阻燃剂的
选择条件
有机高分
[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
[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
[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
[1] DEVASIA R, NAIR C P R, NINAN K N . Solvent and kinetic penultimate unit effects in the copolymerization of acrylonitrile with itaconic acid[J]. European Polymer Journal, 2002,38(10):2003-2010.
doi: 10.1016/S0014-3057(02)00086-1
[2] OUYANG Qin, CHENG Lu, WANG Haojing , et al. Mechanism and kinetics of the stabilization reactions of itaconic acid-modified polyacrylonitrile[J]. Polymer Degradation & Stability, 2008,93(8):1415-1421.
[3] DEVASIA R, NAIR C P R, NINAN K N . Copolymerization of acrylonitrile with itaconic acid in dimethylformamide: effect of triethylamine[J]. European Polymer Journal, 2003,39(3):537-544.
doi: 10.1016/S0014-3057(02)00275-6
[4] ZHANG J, HORROCKS A R, HALL M E . The flammability of polyacrylonitrile and its copolymers IV. The flame retardant mechanism of ammonium polyphosphate[J]. Fire & Materials, 2010,18(5):307-312.
[5] VINCENT Crook, JOHN Ebdon, BARRY Hunt , et al. The influence of comonomers on the degradation and flammability of polyacrylonitrile: design input for a new generation of flame retardants[J]. Polymer Degra-dation & Stability, 2010,95(12):2260-2268.
[6] 王强, 封严 . 聚丙烯腈纤维改性技术及其应用[J]. 合成纤维, 2010,39(1):7-10.
WANG Qiang, FENG Yan . Polyacrylonitrile fiber modification technology and its application[J]. Synthetic Fiber in China, 2010,39(1):7-10.
[7] 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.
doi: 10.1016/j.porgcoat.2017.07.022
[8] 周建红 . 新型阻燃纤维的改性研究[J]. 消防科学与技术, 2014(8):949-951.
ZHOU Jianhong . Study on modification of new flame retardant fibers[J]. Fire Science and Technology, 2014(8):949-951.
[9] 陈胜 . 共混改性阻燃粘胶纤维的制备与性能研究[D]. 成都: 四川大学, 2005: 11.
CHEN Sheng . Preparation and properties of blend modified flame retardant viscose fiber[D]. Chengdu: Sichuan University, 2005: 11.
[10] 李雪艳, 张胜, 张荣 , 等. 中国纤维/织物阻燃技术进展:一[J]. 产业用纺织品, 2011,29(5):1-4.
LI Xueyan, ZHANG Sheng, ZHANG Rong , et al. Progress in flame retardant technology of fiber/fabric in China: I[J]. Technical Textiles, 2011,29(5):1-4.
[11] 方军, 邬国铭 . 非卤系阻燃腈纶[J]. 化纤与纺织技术, 1995(2):25-29.
FANG Jun, WU Guoming . Non-halogen flame retardant acrylic[J]. Chemical Fiber and Textile Technology, 1995(2):25-29.
[12] 张幼维, 赵炯心, 吴承训 . 阻燃腈纶[J]. 合成技术及应用, 1998(2):42-47.
ZHANG Youwei, ZHAO Jiongxin, WU Chengxun . Flame retardant acrylic[J]. Synjournal Technology and Application, 1998(2):42-47.
[13] CHEN Zhuo, DONG Xian, ZHAO Wei , et al. Thermal and flame retardant properties of MWNT reinforced conductive PAN film[J]. Advanced Materials Research, 2014,924:253-259.
doi: 10.4028/www.scientific.net/AMR.924
[14] ZHAO Yaqi, WANG Chengguo, WANG Yanxiang , et al. Aqueous deposited copolymerization of acrylonitrile and itaconic acid[J]. Journal of Applied Polymer Science, 2010,111(6):3163-3169.
doi: 10.1002/app.v111:6
[15] 李建军, 欧育湘 . 阻燃理论[M]. 北京: 科学出版社, 2013: 71-90
LI Jianjun, OU Yuxiang. Flame Retardant Theory[M]. Beijing: Science Press, 2013: 71-90.
[16] GAAN S, SUN G, HUTCHES K , et al. Effect of nitrogen additives on flame retardant action of tributyl phosphate: phosphorus-nitrogen synergism[J]. Polymer Degradation & Stability, 2008,93(1):99-108.
[17] 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.
[18] 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):146-152.
XU Ling, CHENG Bowen, REN Yuanlin , et al. Research progress of flame retardant polyacrylonitrile and its fibers[J]. Journal of Textile Research, 2010,31(8):146-152.
[19] 朱庆松 . 阻燃腈纶的国内开发现状和发展趋势[J]. 纺织科学研究, 2002(4):1-3.
ZHU Qingsong . Domestic development status and development trend of flame retardant acrylic fiber[J]. Textile Science Research, 2002(4):1-3.
[20] WYMAN P, CROOK V, EBDON J , et al. Flame-retarding effects of dialkyl-p-vinylbenzyl phosphonates in copolymers with acrylonitrile[J]. Polymer International, 2010,55(7):764-771.
doi: 10.1002/(ISSN)1097-0126
[21] REN Yuanlin, CHENG Bowen, ZHANG Jinshu , et al. Thermal degradation kinetics of poly (O,O-diethyl-O-allylthiophosphate-co-acrylonitrile) in nitrogen[J]. Journal of Applied Polymer Science, 2010,115(6):3705-3709.
doi: 10.1002/app.v115:6
[22] REN Yuanlin, CHENG Bowen, XU Ling , et al. Fire-retardant copolymer of acrylonitrile with O, O-diethyl-O-allyl thiophosphate[J]. Journal of Applied Polymer Science, 2010,115(3):1489-1494.
doi: 10.1002/app.v115:3
[23] 蒋艾兵, 程博闻, 任元林 , 等. O, O-二乙基丙烯酰基膦酸酯的合成、表征及应用[J]. 精细化工, 2009(2):105-108.
JIANG Aibing, CHENG Bowen, REN Yuanlin , et al. Synjournal, characterization and application of O, O-diethylacryloyl phosphonate[J]. Fine Chemicals, 2009(2):105-108.
[24] 曹堃, 秦一秀, 姚臻 . 腈纶阻燃研究进展[J]. 高分子材料科学与工程, 2008,24(9):1-5.
CAO Kun, QIN Yixiu, YAO Zhen . Research progress of acrylic flame retardant[J]. Polymer Materials Science & Engineering, 2008,24(9):1-5.
[25] 张玉海 . 阻燃聚丙烯腈纤维生产技术[J]. 纺织导报, 2002(3):23-24.
ZHANG Yuhai . Production technology of flame retardant polyacrylonitrile fiber[J]. China Textile Leader, 2002(3):23-24.
[26] BALLISTRERI A, MONTAUDO G, PUGLISI C , et al. Intumescent flame retardants for polymers I. The poly(acrylonitrile)-ammonium polyphosphate-hexabromocyclododecane system[J]. Journal of Applied Polymer Science, 2010,28(5):1743-1750.
doi: 10.1002/app.1983.070280517
[27] 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 Zhao , et al. Preliminary study on blending system of PAN and thiocyanate intercalated hydrotalcite[J]. Journal of Textile Research, 2007,28(5):28-31.
[28] 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 Zhao, YANG Yangong . Kaolinite/polyacrylonitrile intercalation blends: structure and properties[J]. Polymer Materials Science & Engineering, 2008,24(2):111-114.
[29] 任元林, 程博闻, 张金树 , 等. N,N'-二(二乙氧基硫代磷酰基)-1,4-苯二胺的合成、晶体结构及热性能研究[J]. 化学学报, 2007,65(18):2034-2038.
REN Yuanlin, CHENG Bowen, ZHANG Jinshu , et al. Synjournal, crystal structure and thermal properties of N,N'-bis(diethoxythiophosphoryl)-1,4-phenylenedia-mine[J]. Acta Chimica Sinica, 2007,65(18):2034-2038.
[30] 周林, 周绍箕 . 弱酸性阳离子交换纤维的制备和应用的研究[J]. 离子交换与吸附, 1993(6):486-492.
ZHOU Lin, ZHOU Shaoji . Preparation and application of weakly acidic cation exchange Fibers[J]. Ion Exchange and Adsorption, 1993(6):486-492.
[31] 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 flame retardant modified fibers of polyacryloni-trile[J]. Journal of Textile Research, 1988,9(1):5-10.
[32] XU J Z, TIAN C M, MA Z G , et al. Study on the thermal behaviour and flammability of the modified polyacrylonitrile fibers[J]. Journal of Thermal Analysis and Calorimetry, 2000,63(2):501-506.
doi: 10.1023/A:1010181618305
[33] 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 acrylic fabric with cyanide hydrolase/zinc borate[J]. Journal of Textile Research, 2016,37(3):110-113.
[34] AKOVALI G, GUNDOGAN G . Studies on flame retardancy of polyacrylonitrile fiber treated by flame-retardant monomers in cold plasma[J]. Journal of Applied Polymer Science, 1990,41(9/10):2011-2019.
doi: 10.1002/app.1990.070410907
[35] TSAFACK M J, LEVALOIS-GRUTZMACHER J . Plasma-induced graft-polymerization of flame retardant monomers onto PAN fabrics[J]. Surface & Coatings Technology, 2006,200(11):3503-3510.
[36] ABENOJAR J, TORREGROSACOQUE, MARTINEZ M A , et al. Surface modifications of polycarbonate (PC) and acrylonitrile butadiene styrene (ABS) copolymer by treatment with atmospheric plasma[J]. Surface & Coatings Technology, 2009,203(16):2173-2180.
[37] REN Yuanlin, GU Yetong, ZENG Qian , et al. UV-induced surface grafting polymerization for preparing phosphorus-containing flame retardant polyacrylonitrile fabric[J]. European Polymer Journal, 2017,94:1-10.
doi: 10.1016/j.eurpolymj.2017.06.037
[38] 张玉海 . 阻燃聚丙烯腈纤维生产技术现状[J]. 纺织导报, 2002,10(3):23-24.
ZHANG Yuhai . Current situation of production technology of flame retardant polyacrylonitrile fiber[J]. China Textile Leader, 2002,10(3):23-24.
[39] SHINDO A . Some properties of PAN-based carbon fiber[J]. Journal of the Ceramic Society of Japan, 2000,108:35-40.
[40] 张丽春 . 共聚单体对聚丙烯腈预氧化的影响[D]. 长春:长春工业大学, 2015: 6-7.
ZHANG Lichun . Effect of copolymer on preoxidation of polyacrylonitrile[D]. Changchun: Changchun University of Technology, 2015: 6-7.
[41] RAHAMAN M S A, ISMAIL A F, MUSTAFA A . A review of heat treatment on polyacrylonitrile fiber[J]. Polymer Degradation & Stability, 2007,92(8):1421-1432.
[42] CROOK V, EBDON J, HUNT B , et al. The influence of comonomers on the degradation and flammability of polyacrylonitrile: design input for a new generation of flame retardants[J]. Polymer Degradation & Stability, 2010,95(12):2260-2268.
[43] XUE Yan, LIU Jie, LIAN Feng , et al. Effect of the oxygen-induced modification of polyacrylonitrile fibers during thermal-oxidative stabilization on the radial microcrystalline structure of the resulting carbon fibers[J]. Polymer Degradation & Stability, 2013,98(11):2259-2267.
[44] 王成国, 朱波 . 聚丙烯腈基碳纤维[M]. 北京: 科学出版社, 2011: 281.
WANG Chengguo, ZHU BO. Polyacrylonitrile-based Carbon Fiber [M]. Beijing: Science Press, 2011: 281.
[45] 陈兵 . 纤维阻燃技术现状与进展[J]. 现代纺织技术, 1999(3):31-35.
CHEN Bing . Current status and progress of fiber flame retardant technology[J]. Advanced Textile Technology, 1999(3):31-35.
[46] 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 Chang , et al. Study on phosphorus and nitrogen intumescent flame retardant finishing of acrylic fiber[J]. Wool Textile Journal, 2016,44(12):31-33.
[47] REN Yuanlin, ZHANG Yue, ZHAO Jieyun , et al. Phosphorus-doped organic-inorganic hybrid silicon coating for improving fire retardancy of polyacrylonitrile fabric[J]. Journal of Sol-Gel Science and Technology, 2017,82:280-288.
doi: 10.1007/s10971-016-4273-z
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[1] . [J]. JOURNAL OF TEXTILE RESEARCH, 2000, 21(05): 31 -33 .
[2] . [J]. JOURNAL OF TEXTILE RESEARCH, 1987, 8(11): 40 -41 .
[3] LIU Hao;CHENG Ling. Quality evaluation of knitting yarns using modified FKCM[J]. JOURNAL OF TEXTILE RESEARCH, 2009, 30(01): 37 -41 .
[4] . [J]. JOURNAL OF TEXTILE RESEARCH, 1993, 14(04): 26 -30 .
[5] . [J]. JOURNAL OF TEXTILE RESEARCH, 1983, 4(11): 52 .
[6] . [J]. JOURNAL OF TEXTILE RESEARCH, 1983, 4(12): 26 -30 .
[7] . [J]. JOURNAL OF TEXTILE RESEARCH, 1983, 4(12): 51 .
[8] Jie YU. Structure and properties of polyacrylonitrile / Ca-montmorillonite nanocomposite fiber[J]. JOURNAL OF TEXTILE RESEARCH, 2011, 32(5): 29 -32 .
[9] . [J]. JOURNAL OF TEXTILE RESEARCH, 1982, 3(01): 58 .
[10] L Libin;DU Mei;ZHAO Lei. Tensile properties analysis of polyester/cotton/silk tri-component Sirofil composite yarn[J]. JOURNAL OF TEXTILE RESEARCH, 2007, 28(6): 45 -47 .