The flammability of polyacrylonitrile and its copolymers III. Effect of flame retardants

This paper extends previously reported work ^1,2 and describes the influence that a range of selected flame retardants have on the burning behaviour and pyrolyses of homo-and copolymers of acrylonitrile. Various inorganic and organic phosphorus and nitrogen- or sulphur-containing, halogen-containing (in the absence and presence of halogen or antimony (III) oxide) and nitrogen-containing flame retardants and red phosphorus were studied using LOI, TGA, DSC and residual char measuring techniques. Flame retardancy relates directly to char-forming tendency for all retardants and their ability to reduce the dominance of flammable volatiles formed during the first stage of acrylic polymer pyrolysis. Ammonium phosphates are particularly effective flame retardants for the selected copolymers. Possible mechanisms of retardant activity are discussed, including the char-forming tendency of antimony–bromine combiniations.     

聚丙烯纤维阻燃剂应用研究进展

绍了聚丙烯(PP)阻燃剂的种类及其在PP纤维中的应用。PP阻燃剂有含磷、含卤、含硅、金属氢氧化物及其氧化物以及纳米复合材料;讨论了阻燃剂的性能和提高阻燃效果的方法;提出新型阻燃剂必将朝着无卤、消烟的复合型阻燃剂方向发展     

PC/ABS合金用阻燃体系的研究进展

综述了国内外用于PC/ABS合金的阻燃体系如卤系、磷-卤系、磷系以及非磷非卤等的发展现状与研究进展,并简要介绍了相关阻燃机理及将来的发展方向。目前,PC/ABS合金用的阻燃体系的开发正朝向高效化、多功能化、环保化发展,提高阻燃效率、减少用量、降低对健康和环境的危害,已越来越引起人们重视,非卤阻燃PC/ABS合金用的非卤阻燃剂已成为开发、应用的主要趋势。     

阻燃PBT的耐侯性能研究

考察了溴系阻燃剂、磷氮系阻燃剂对聚对苯二甲酸丁二醇酯（PBT）力学性能、耐光老化性能的影响，还研究了酸吸收剂对阻燃PBT材料的力学性能、紫外线稳定性的影响。结果表明，钙锌稳定剂能提高卤系阻燃材料的耐侯性能，无卤阻燃PBT的耐侯性能优于卤系阻燃PBT（1000h，△E≤3）。     

涤纶阻燃技术研究进展

综述了聚酯纤维阻燃化处理方法,分析了卤系和磷系阻燃剂及其对聚酯的阻燃改性作用,以及聚酯/无机纳米复合材料的热稳定性与阻燃性。指出:磷系共聚阻燃改性技术辅以其它反应性单体、纳米添加剂等有利于改善涤纶的抗熔滴性和炭化阻燃作用。     

含磷阻燃剂的应用研究进展

磷系阻燃剂作为一种高效、无烟、低毒、无污染的阻燃剂,备受研究者关注,已经在合成和应用等方面取得了显著成就。本文对近年来磷系阻燃剂的阻燃机理及应用进展作了简要综述,分别对新型含磷阻燃剂在聚氨酯、聚氨基甲酸乙酯泡沫、环氧树脂、多酯类与尼龙在这四方面的应用来说明含磷阻燃剂最近的研究进展,例如:RXP在聚氨酯上的应用,DEEP在聚氨基甲酸乙酯泡沫上的应用等。     

Interaction of a phosphorus‐based FR,a nanoclay and PA6. Part 2 interaction of the complete PA6 polymer nanocomposites

Polyamide 6 (PA6) is modified with a nanoclay (NC), Cloisite 30B and/or a flame retardant (FR), OP1311. The thermal decomposition of pure PA6 and PA6 nanocomposites is done by thermogravimetric analysis (TGA). The decomposition products from TGA in nitrogen and air are analysed online by Fourier transform infrared (FTIR) spectroscopy in order to examine the time/temperature‐dependent thermal degradation processes and monitor the evolved gases online. The profiles of the evolved gases are compared with ε‐caprolactam spectra, which are the main species in the gas phase. Results show that the addition of the fire retardant decreases the degradation temperature, whereas the incorporation of NC (PA6+NC) contributes to increased residual mass and char formation. The evolved gases from TGA‐FTIR in nitrogen from pure PA6 and (PA6+NC) are hydrocarbons, carbon dioxide, water, ε‐caprolactam and ammonia. The (PA6+FR) and (PA6+NC+FR) evolve the same volatiles with an additional phosphorus‐containing species, namely diethylphosphinic acid. The thermo‐oxidative degradation of all these composites in air yields carbon monoxide with an increased production of carbon dioxide, water and hydrogen cyanide. Another important result is that the hydrogen cyanide does not increase when the phosphinate FR is used. Copyright © 2009 John Wiley & Sons, Ltd.     

磷-胺-醛树脂型阻燃剂处理落叶松的热分析及其动力学

将落叶松用一系列磷-胺-醛树脂型阻燃剂进行阻燃处理,所得阻燃落叶松采用热分析、锥形量热研究其热解行为,用氧指数、剩炭率、热释放速率、总热释放量等参数表征它的阻燃性能,并用Broido方程计算落叶松的动力学参数. 结果发现,阻燃落叶松氧指数、剩炭率增加,热释放速率、总热释放量降低,表明经阻燃剂处理的落叶松燃烧性降低. 落叶松经阻燃剂处理后,热解活化能降低很多,表明阻燃剂对落叶松热解具有催化作用,其主要热解阶段在低于300℃进行. 在此温度下,落叶松热解主要发生脱水、重排交联炭化反应,产生水、CO及CO2、固体残渣,可燃性气体大大降低,达到降低落叶松燃烧性的目的.     

反应型含磷阻燃剂的应用研究进展

含磷阻燃剂具有低烟无毒、阻燃效果好的特点,是典型的无卤阻燃剂。本文阐述了含磷阻燃剂的阻燃机理,综述了将反应型含磷阻燃剂引入聚氨酯、环氧树脂和丙烯酸树脂等体系中所采用的不同改性方法,这些反应型阻燃聚合物均是主链或侧链含磷。本文还对近几年来国内外关于含磷阻燃剂在这些体系中的应用研究进展进行了概述,提出未来应加深对阻燃剂协同机理及含磷阻燃剂水性化和光固化的研究。     

主链含三芳基氧化膦的阻燃工程塑料

叙述反应型磷系阻燃剂双（４－羧苯基）苯基氧化膦和双（４－羟苯基）苯基氧化膦故土的合成,以及以三芳基氧化膦为链段的含磷阻燃尼龙６６共聚物、共聚碳酸酯及聚芳酯的合成方法,讨论了按上述方法合成的阻燃工程塑料的阻燃性能     

无卤阻燃PC及PC／ABS合金研究进展

结合飞机使用的聚碳酸酯(PC)及PC/(丙烯腈/丁二烯/苯乙烯)共聚物(ABS)合金,综述了2000年以来国内外有关PC、PC/ABS合金用无卤阻燃剂的研究进展,包括舍磷阻燃剂、含硅阻燃剂、含硫阻燃剂和纳米阻燃技术等,介绍了它们的阻燃效果和阻燃机理等.指出采用含硅阻燃剂阻燃飞机部件用PC及PC/ABS合金是必然趋势.     

Localized radiation grafting of flame retardants to polyethylene terephthalate. II. Vinyl phosphonates

Six vinyl phosphonates have been synthesized and evaluated as grafts on poly(ethylene terephthalate) for their flame retardance properties. Diethylvinyl phosphonate was used as a model for phosphorus-containing flame retardants in developing the methodology for localizing flame retardants either on the surface of the filament or uniformly throughout it. SEM–X-ray microprobe techniques were used in the verification of the location of the flame retardant in the filament. The flame retardance efficiency of poly(diethyl vinyl phosphonate) was then correlated with its location in the filament. Other grafted phosphorus-containing flame retardants showed a range of efficiencies that depended not only upon the location of the graft within the filament but also upon the %P in the compound. The wide variations in flame retardance efficiencies of copolymers and terpolymers were attributed to large variations in the melt viscosity of the different grafted materials. The grafts showed only small changes in tenacity and large increases in elongation.     

Synthesis of phosphorus-containing flame retardants and investigation of their flame retardant behavior in textile applications

Flame retardants are a growing area of research interest. Nonhalogenated, durable, and nonleachable flame retardants are one of the main strategies used in the research of flame retardant polymers. In this regard, the covalent attachment of phosphorus-containing flame retardants onto cotton fabric has been developed. Two types of reactive phosphorus-containing flame retardants (MKT-1 and MKT-2) have been synthesized and used as a surface coating for cotton fabric. MKT-1 possesses anhydride and acid functionalities that can react with the  OH functionalities in cellulose. In addition, MKT-2 has both acid and organosilicon groups that can also react with the hydroxy group present in cellulose. The structures of the reactive flame retardants (MKT-1 and MKT-2) were characterized using ¹³C and ³¹P nuclear magnetic resonance spectroscopy. Thermal properties of the coated and uncoated cotton fabrics were investigated using thermogravimetric analysis. Surface characterization was carried out using scanning electron microscopy and X-ray photoelectron spectroscopy. A standard test method used to evaluate the flammability of blankets (BS 5852) was also applied to characterize the fire retardant properties of the coated and uncoated cotton fabrics studied. Different loadings of MKT-1 and MKT-2 on the fabric (10, 20, and 30% by weight in dimethylformamide solution) were applied in the dip coating process. The cotton fabric coated with 30% MKT-2 does not burn after being subjected to a propane burner for 20 s and also produced the highest char yield (36%) at 500 °C. Inductively coupled plasma–optical emission spectrometry showed that MKT-1 contains 8.23 ± 0.33 P% whereas MKT-2 contains 3.88 ± 0.15 P%. Although MKT-1 possess a higher P content than MKT-2, the additive effect caused by the organosilicon and nitrogen groups present in MK-2 enhance its flame retardant properties. Furthermore, the covalently attached flame retardant materials are durable and do not hydrolyze during washing. The mechanical properties of coated fabrics were characterized by a tensile test and significant change in elongation at break was observed. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47935.     

用于环氧树脂的复合阻燃剂响应面优化研究

将环氧树脂E44作为基体,添加9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、超细氢氧化铝(ATH)、三聚氰胺氰尿酸盐(MCA)3种阻燃剂,探究三者在环氧树脂中使其性能达到最优时的最佳配比。通过单因素试验,探究每种阻燃剂的最优用量,再用Design-Expert软件设计3因素3水平的响应面优化试验,将3种阻燃剂进行复配,以氧指数和拉伸强度作为响应值,得到拟合曲线后对最优值进行验证。结果表明:DOPO,ATH,MCA质量分数分别为5.73%,20.00%,8.28%(以环氧树脂计)时,复合阻燃环氧树脂材料具有最佳性能,其极限氧指数(LOI)为31.2%、拉伸强度为28.20 MPa。     

阻燃型木塑复合材料研究进展

综述了近年来阻燃型木塑复合材料的研究成果.分析了木塑复合材料的燃烧特性,并总结了铝-镁系阻燃剂、膨胀型阻燃剂、磷系阻燃剂及纳米粒子阻燃剂等无卤阻燃剂对木塑复合材料的阻燃性能和力学性能的影响;结合木塑复合材料阻燃过程中存在的问题对其研究的趋势进行了展望.     

膨胀型阻燃剂的疏水改性及对水性阻燃涂料性能的影响

为了提高水性阻燃涂层的耐水性,以环氧树脂(EP)作为包覆材料,分别采用单一组分和混合组分改性两种工艺对阻燃剂〔聚磷酸铵(APP)、三聚氰胺(MEL)和季戊四醇(PER)〕进行包覆改性,制备出了改性阻燃剂及水性阻燃涂层。借助FTIR分析阻燃剂表面基团;采用SEM观察其微观结构;测量阻燃剂的接触角,并对其粒度分布进行统计;借助TG对阻燃剂及水性阻燃涂层进行测试;并参考国标GB/T1733—1993对涂层耐水性进行了测试。结果表明:两种工艺制备的阻燃剂其表面均包覆EP,且EP用量为阻燃剂质量的15%时,疏水效果达到最佳;阻燃剂经改性后其溶解度降低,接触角增大,使水性阻燃涂层耐水性显著提高,且阻燃剂采用混合组分改性效率更高;聚磷酸铵与EP发生交联生成不饱和富碳结构,加固残炭碳骨架的稳定性及增加涂层残余物的质量。     

邻苯二胺基环三磷腈阻燃剂在EVA材料中的性能及机理研究

应用混料设计实验方法研究了邻苯二胺基环三磷腈(HACTP)和聚磷酸铵(APP)、蒙脱土(MMT)复配阻燃剂对乙烯-醋酸乙烯酯共聚物(EVA)材料阻燃和力学性能的影响,并利用锥形量热仪及电子扫描显微镜研究了不同配方下阻燃EVA的热释放性能和燃烧后膨胀炭层的微观形貌,探讨阻燃机理.结果 表明:在HACTP质量分数为32.8...     

尼龙6/有机蒙脱土阻燃复合材料的结构与性能

将尼龙6、有机蒙脱土和阻燃剂（氢氧化镁、氨基硅油、十溴联苯醚和三氧化二锑、三聚氰胺焦磷酸盐、三聚氰胺磷酸盐）通过熔融插层法直接制备了尼龙6／有机蒙脱土阻燃复合材料。通过X射线衍射（XRD）、力学性能测试、极限氧指数（LOI）测试研究了蒙脱土在复合材料内的分散、复合材料的力学性能以及阻燃性能。结果表明：氨基硅油与有机蒙脱土具有阻燃协同效应，当氨基硅油和有机蒙脱土质量分数分别为2％和5％时，复合材料的LOI高达34％。氢氧化镁、氨基硅油与有机蒙脱土三者具有极强的阻燃协同效应，当氢氧化镁用量分别为30％、40％、50％时，阻燃复合材料的LOI分别为63％、60％、70％。     

无卤阻燃聚对苯二甲酸丙二酯的研究

使用无卤磷系阻燃剂二乙基次膦酸铝(ADP)和氮系阻燃剂三聚氰胺氰尿酸盐(MCA)作为阻燃剂,马来酸酐接枝聚烯烃弹性体(POE-g-MAH)为增韧剂,对聚对苯二甲酸丙二酯(PTT)进行阻燃改性,分别研究两种不同体系阻燃剂对PTT阻燃性能和力学性能的影响,并通过热失重(TG)分析仪、差示扫描量热(DSC)仪,扫描电子显微镜(SEM)对其阻燃机理进行研究。实验结果表明,添加质量分数10%的ADP时,阻燃PTT达到V–0级,极限氧指数(LOI)达到30.0%,ADP主要在凝聚相中发挥阻燃作用;添加质量分数20%的MCA时,阻燃PTT达到V–0级,LOI达到24.9%,MCA主要在气相中发挥阻燃作用;ADP与MCA的加入都降低了阻燃PTT的综合力学性能。TG和DSC测试结果说明,ADP与PTT间的相容性良好,可以有效地促进PTT成炭并提高材料的阻燃性能;MCA与PTT间的相容性较差,且MCA对PTT成炭没有影响。添加质量分数5%的ADP和10%的MCA时,阻燃PTT达到V–0级,LOI达到26.9%,说明ADP与MCA具有协效阻燃作用。     

用于超纤革PU浆料的无卤阻燃改性

选择了有机磷系和磷氮协同两种不同的无卤阻燃剂与溶剂型PU进行共混制备无卤阻燃PU,对其力学性能、阻燃性能及耐碱性能进行了系统研究。结果发现:相较于磷氮协同阻燃剂(SN-605),采用有机磷系阻燃剂(JL-30)改性PU显示出更好的阻燃性能与耐碱性能;当阻燃剂质量分数为11.1%时,阻燃PU的LOI可以达到29.1%,垂直燃烧测试达到V-0级;并且具有较好的耐碱性能,在90℃、30 g/L NaOH溶液中碱处理40 min后,其LOI仍然可以达到28.7%,垂直燃烧测试等级没有下降;但两种阻燃剂的加入均会使PU的抗张强度出现不同程度的下降。此外,热失重测试(TG)显示,两种阻燃PU的阻燃机制不同,JL阻燃剂的加入使PU的热分解温度降低,并且在800℃时的残炭量没有明显增加,呈现明显的气相阻燃机制;而SN阻燃剂的加入使PU的残炭量明显增加,呈现明显的凝聚相阻燃机制。