新型无卤聚合物阻燃剂的研究进展
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摘要
为提高阻燃纺织品的阻燃耐久性、耐水洗性,避免传统的卤系阻燃剂在高温下产生二噁英、卤化氢等二次污染物,采用无卤聚合物阻燃剂是行之有效的方法之一。阐述了含磷、氮、硅等阻燃元素的一系列支链型、直链型和交联型聚合物阻燃剂及其单体,主要介绍了磷(膦)酸酯、磷(膦)酰胺、含磷聚硅氧烷、生物基阻燃剂等聚合物型阻燃剂类型、结构、合成、性能及其在纺织品中的应用;分析了当前纺织品用阻燃剂存在的问题。认为耐久性阻燃剂应集中在磷-氮含量高、具有反应活性的绿色环保阻燃剂的合成,要加大多组分阻燃剂复合协同机制研究,加快现代物理整理技术的研究。
In order to improve the durability and washable resistance of flame retardant textiles,and avoid the generation of secondary pollutants such as dioxins and hydrogen halides at high temperature for conventional halogenated flame retardants,using halogen-free polymer flame retardant is one of the effective methods. This paper systematically described a series of branched,linear and crosslinked polymer flame retardants and their monomers containing flame retardant elements such as phosphorus,nitrogen and silicon. The types,structures,synthesis,properties and applications of polymer flame retardants such as phosphates( phosphonates), phosphoramides( phosphonamides), phosphoruscontaining polysiloxane and bio-based flame retardants were mainly introduced. The current problems of flame retardants for textiles were analyzed. It was pointed out that the durable flame retardant should focus on the synthesis of eco-friendly flame retardants with high phosphorus-nitrogen content and high reactivity,and should increase the research on synergistic mechanism of multi-component compounds,and accelerate the research direction of modern physical finishing technology research.
In order to improve the durability and washable resistance of flame retardant textiles,and avoid the generation of secondary pollutants such as dioxins and hydrogen halides at high temperature for conventional halogenated flame retardants,using halogen-free polymer flame retardant is one of the effective methods. This paper systematically described a series of branched,linear and crosslinked polymer flame retardants and their monomers containing flame retardant elements such as phosphorus,nitrogen and silicon. The types,structures,synthesis,properties and applications of polymer flame retardants such as phosphates( phosphonates), phosphoramides( phosphonamides), phosphoruscontaining polysiloxane and bio-based flame retardants were mainly introduced. The current problems of flame retardants for textiles were analyzed. It was pointed out that the durable flame retardant should focus on the synthesis of eco-friendly flame retardants with high phosphorus-nitrogen content and high reactivity,and should increase the research on synergistic mechanism of multi-component compounds,and accelerate the research direction of modern physical finishing technology research.
引文
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[23]王琦.棉用无甲醛阻燃剂的合成及应用[D].上海:东华大学,2014:33-37.WANG Qi. Cotton with formaldehyde-free flame retardant synthesis and application[D]. Shanghai:Donghua University,2014:33-37.
[24]董振泉.磷酸酯阻燃剂PPAP的制备及其在纯棉织物上的应用研究[D].上海:东华大学,2011:33-38.DONG Zhenquan. Preparation of phosphate flame retardant PPAP and its application in pure cotton fabric[D]. Shanghai:Donghua University,2011:33-38.
[25]周向东,陈迎春,蒲泽佳,等.锦纶用耐久性阻燃剂的合成与应用[J].成都纺织高等专科学校学报,2016,33(1):37-41.ZHOU Xiangdong,CHEN Yingchun,PU Zejia,et al.Synthesis and application of durable flame retardant for polyamide[J]. Journal of Chengdu Textile College,2016,33(1):37-41.
[26]杨敏芬.有机磷系阻燃剂的合成及其在尼龙中的应用[D].杭州:浙江理工大学,2015:28-30.YANG Minfen. Synthesis of organic phosphorus flame retardants and its application in nylon[D]. Hangzhou:Zhejiang Sci-Tech University,2015:28-30.
[27]蒋立,丁斌,郝凤岭,等.环三磷腈类阻燃剂的研究现状[J].印染助剂,2017,34(4):6-11.JIANG Li,DING Bin,HAO Fengling,et al. Research status of cyclotriphosphazene flame retardants[J].Textile Auxiliaries,2017,34(4):6-11.
[28]高维全,唐淑娟,孙德,等.羟基环三磷腈衍生物阻燃剂的合成和性能研究[J].染整技术,2008,30(9):11-14,59.GAO Weiquan,TANG Shujuan,SUN De,et al. Studies on the synthesis and properties of hydroxyl cyclotriphosphazene derivatives flame retardant[J].Dyeing and Finishing Technology,2008,30(9):11-14,59.
[29]陈文杰,胡毅,许春磊,等.棉织物架桥型水性聚氨酯-NPAZ阻燃整理[J].印染,2010,36(24):1-3.CHEN Wenjie, HU Yi, XU Chunlei, et al. Flame retardant finishing of waterborne polyurethane-NPAZ cotton fabric bridge[J]. China Dyeing&Finishing,2010,36(24):1-3.
[30] LI Q L,HUANG F Q,JIANG X J. Preparation and properties of a washable flame-retardant coated fabric[J]. Indian Journal of Fibre&Textile Research,2016,41:40-46.
[31]王立春.新型含磷阻燃剂的合成及无卤阻燃交联EVA复合材料的制备与性能研究[D].上海:上海交通大学,2011:47-50.WANG Lichun. Synthesis of a new phosphoruscontaining flame retardant and halogen-free flame retardant cross-linked EVA composite material preparation and performance[D]. Shanghai:Shanghai Jiao Tong University,2011:47-50.
[32] ZHONG H,WEI P,JIANG P,et al. Synthesis and characteristics of a novel silicon-containing flame retardant and its application in poly[2, 2-propane-(bisphenol)carbonate]/acrylonitrile butadiene styrene[J]. Journal of Polymer Science Part B:Polymer Physics,2007,45(13):1542-1551.
[33] BOSCO F,CARLETTO R A,ALONGI J,et al.Thermal stability and flame resistance of cotton fabrics treated with whey proteins[J]. Carbohydrate Polymers,2013,94:372-377.
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[2] HORROCKS A R,WEI L. Recent developments and challenges in flame retardation of textiles and fibres[J].Materials China,2015,54(9):56-60.
[3]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 on new technology of fabric flame retardant coating[J]. Journal of Textile Research,2017,38(9):168-173.
[4] KOCH C,SCHMIDT-KOTTER S T,RUPP R,et al.Review of hexabromocyclododecane(HBCD)with a focus on legislation and recent publications concerning toxicokinetics and-dynamics[J]. Environmental Pollution,2015,199:26-34.
[5]李强林,黄方千,杨东洁,等.冷等离子体接枝聚合阻燃改性纺织品研究进展[J].成都纺织高等专科学校学报,2015,32(4):12-16.LI Qianglin,HUANG Fangqian,YANG Dongjie,et al.Research progress on flame retardant modified textile by cold plasma graft polymerization[J]. Journal of Chengdu Textile Colloge,2015,32(4):12-16.
[6]李娜娜,姜国伟,周光远,等.有机磷类阻燃剂的合成及应用进展[J].应用化学,2016,33(6):611-623.LI Nana,JIANG Guowei,ZHOU Guangyuan,et al.Synthesis and application of organic phosphorus flame retardants[J]. Chinese Journal of Applied Chemistry,2016,33(6):611-623.
[7]李博,李强林.含磷聚合物阻燃剂研究进展[J].成都纺织高等专科学校学报,2014,31(1):21-25.LI Bo,LI Qianglin. Research progress on phosphoruscontaining polymer flame retardant[J]. Journal of Chengdu Textile College,2014,31(1):21-25.
[8] LI Q L,WANG X L,WAND D Y,et al. Durable flame retardant finishing of PET/cotton blends using a novel PVA-based phosphorus-nitrogen polymer[J]. Journal of Applied Polymer Science,2011,122(1):342-353.
[9]王灿灿.磷酸酯阻燃剂的合成及其在黄麻织物上的应用[D].太原:太原理工大学,2012:25-27.WANG Cancan. Synthesis of phosphate flame retardant and its application in jute fabric[D]. Taiyuan:Taiyuan University of Technology,2012:25-27.
[10] YOSHIOKA T M,CONDON B D,CINTRN M S,et al. Enhanced flame retardant property of fiber reactive halogen-free organophosphonate[J]. Industrial&Engineering Chemistry Research, 2012, 51(34):11031-11037.
[11]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.
[12]王斐,邓启刚,陈朝晖,等.亚麻用降解壳聚糖含磷阻燃剂的合成及应用[J].精细化工,2015,32(4):461-465.WANG Fei, DENG Qigang, CHEN Zhaohui, et al.Synthesis and application of flame retardant for degradation of flax in chitosan[J]. Fine Chemicals,2015,32(4):461-465.
[13]林锐彬,李战雄,赵言,等.环三磷腈丙烯酸酯合成及其在棉织物阻燃整理中的应用[J].印染助剂,2010,27(4):25-28.LIN Ruibin, LI Zhanxiong, ZHAO Yan, et al.Cyclotriphosphazene acrylate synthesis and its application in cotton fabric flame retardant finishing[J].Dyeing Auxiliaries,2010,27(4):25-28.
[14]钱立军,叶龙健,韩鑫磊,等.基于磷杂菲基团化合物的构建与性能[J].化学进展,2010,22(9):1776-1783.QIAN Lijun, YE Longjian, HAN Xinlei, et al.Construction and properties of phosphaphenanthrene based compounds[J]. Progress in Chemistry,2010,22(9):1776-1783.
[15]金崇业,贾丽霞.有机磷阻燃剂在羊毛纺织品中的应用和发展[J].纺织导报,2015,31(4):32-35.JIN Chongye,JIA Lixia. Application and development of the organic phosphorus flame retardant for wool fabric[J]. China Textile Leader,2015,31(4):32-35.
[16]帅博旺.新型丙烯酸酯聚合物的合成及其在棉织物上的应用研究[D].上海:东华大学,2012:25-38,77-80.SHUAI Bowang. New acrylic polymer synthesis and its application in cotton fabric[D]. Shanghai:Donghua University,2012:25-38,77-80.
[17]董朝红.棉用含磷氮元素聚硅氧烷阻燃剂的制备及性能研究[D].无锡:江南大学,2014:37-38,50-52.DONG Chaohong. Preparation and properties of polysiloxane flame retardants containing phosphorus and nitrogen for cotton[D]. Wuxi:Jiangnan University,2014:37-38,50-52.
[18] HORROCKS A R. Flame retardant challenges for textiles and fibres:new chemistry versus innovatory solutions[J]. Polymer Degradation&Stability, 2011,96(3):377-392.
[19] LIU W,CHEN L,WANG Y Z. A novel phosphoruscontaining flame retardant for the formaldehyde-free treatment of cotton fabrics[J]. Polymer Degradation&Stability,2012,97(12):2487-2491.
[20]周羿凝,许苗军,孙才英. N-羟甲基丙烯酰胺螺环磷酸酯的合成及表征[J].精细化工,2015,32(8):917-920.ZHOU Yining,XU Miaojun,SUN Caiying. Preparation and characterization of N-methylolacrylamide spiro phosphates[J]. Fine Chemicals,2015,32(8):917-920.
[21]陈金玲.涤纶用有机磷阻燃水性聚氨酯涂层胶的制备及应用研究[D].杭州:浙江理工大学,2013:13-16,39-45.CHEN Jinling. Polyester with organic phosphorus flame retardant water-based polyurethane coating adhesive preparation and application[D]. Hangzhou:Zhejiang Sci-Tech University,2013:13-16,39-45.
[22]李强林,黄方千,魏玉君,等.涤棉织物的金属离子改性聚磷酸铵阻燃整理[J].印染,2017,43(19):11-16.LI Qianglin,HUANG Fangqian,WEI Yujun, et al.Metal ion modified ammonium polyphosphate flame retardant finishing of polyester/cotton fabric[J]. China Dyeing&Finishing,2017(19):11-16.
[23]王琦.棉用无甲醛阻燃剂的合成及应用[D].上海:东华大学,2014:33-37.WANG Qi. Cotton with formaldehyde-free flame retardant synthesis and application[D]. Shanghai:Donghua University,2014:33-37.
[24]董振泉.磷酸酯阻燃剂PPAP的制备及其在纯棉织物上的应用研究[D].上海:东华大学,2011:33-38.DONG Zhenquan. Preparation of phosphate flame retardant PPAP and its application in pure cotton fabric[D]. Shanghai:Donghua University,2011:33-38.
[25]周向东,陈迎春,蒲泽佳,等.锦纶用耐久性阻燃剂的合成与应用[J].成都纺织高等专科学校学报,2016,33(1):37-41.ZHOU Xiangdong,CHEN Yingchun,PU Zejia,et al.Synthesis and application of durable flame retardant for polyamide[J]. Journal of Chengdu Textile College,2016,33(1):37-41.
[26]杨敏芬.有机磷系阻燃剂的合成及其在尼龙中的应用[D].杭州:浙江理工大学,2015:28-30.YANG Minfen. Synthesis of organic phosphorus flame retardants and its application in nylon[D]. Hangzhou:Zhejiang Sci-Tech University,2015:28-30.
[27]蒋立,丁斌,郝凤岭,等.环三磷腈类阻燃剂的研究现状[J].印染助剂,2017,34(4):6-11.JIANG Li,DING Bin,HAO Fengling,et al. Research status of cyclotriphosphazene flame retardants[J].Textile Auxiliaries,2017,34(4):6-11.
[28]高维全,唐淑娟,孙德,等.羟基环三磷腈衍生物阻燃剂的合成和性能研究[J].染整技术,2008,30(9):11-14,59.GAO Weiquan,TANG Shujuan,SUN De,et al. Studies on the synthesis and properties of hydroxyl cyclotriphosphazene derivatives flame retardant[J].Dyeing and Finishing Technology,2008,30(9):11-14,59.
[29]陈文杰,胡毅,许春磊,等.棉织物架桥型水性聚氨酯-NPAZ阻燃整理[J].印染,2010,36(24):1-3.CHEN Wenjie, HU Yi, XU Chunlei, et al. Flame retardant finishing of waterborne polyurethane-NPAZ cotton fabric bridge[J]. China Dyeing&Finishing,2010,36(24):1-3.
[30] LI Q L,HUANG F Q,JIANG X J. Preparation and properties of a washable flame-retardant coated fabric[J]. Indian Journal of Fibre&Textile Research,2016,41:40-46.
[31]王立春.新型含磷阻燃剂的合成及无卤阻燃交联EVA复合材料的制备与性能研究[D].上海:上海交通大学,2011:47-50.WANG Lichun. Synthesis of a new phosphoruscontaining flame retardant and halogen-free flame retardant cross-linked EVA composite material preparation and performance[D]. Shanghai:Shanghai Jiao Tong University,2011:47-50.
[32] ZHONG H,WEI P,JIANG P,et al. Synthesis and characteristics of a novel silicon-containing flame retardant and its application in poly[2, 2-propane-(bisphenol)carbonate]/acrylonitrile butadiene styrene[J]. Journal of Polymer Science Part B:Polymer Physics,2007,45(13):1542-1551.
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