聚丙烯膨胀型阻燃剂研究进展

膨胀型阻燃剂是一类环保型阻燃剂,目前用于聚丙烯的膨胀型阻燃剂在国内外己开展了大量的研究工作。综述了近年来国内外聚丙烯的膨胀型阻燃剂的研究进展以及相关的硅烷协效剂、金属协效剂和其它一些协效剂在阻燃体系中的应用,并对研发具有优良阻燃性能和力学性能的聚丙烯膨胀型阻燃剂的一些研究思路进行了归纳和介绍。     

聚丙烯用化学膨胀型阻燃剂研究进展

综述了聚丙烯用化学膨胀型阻燃剂的研究进展,介绍了无机阻燃协效剂、新型成炭剂在含聚磷酸铵膨胀阻燃聚丙烯体系中的应用效果,以及新型化学膨胀型阻燃剂在聚丙烯中的使用情况。     

膨胀型阻燃涂料的制备及性能研究

以聚磷酸铵(APP)、三聚氰胺(MEL)和季戊四醇(PER)作为膨胀型阻燃剂,可膨胀石墨为阻燃协效剂,硅丙乳液为成膜物质,钛白粉为颜填料,水为溶剂制备出了一种可用于铁丝网的环保膨胀型阻燃涂料。通过正交试验确定了膨胀型阻燃剂的最佳配比;通过单一变量因素对成膜物质、阻燃协效剂种类进行了筛选,并对其最佳添加量进行了优化。结果表明:当硅丙乳液的添加量为30%,聚磷酸铵∶三聚氰胺∶季戊四醇∶可膨胀石墨质量比为20∶15∶13∶2时,所制备的膨胀型阻燃涂料具有较好的阻燃性能。     

改性聚磷酸铵对三嗪类膨胀阻燃聚丙烯性能的影响

由改性聚磷酸铵(APP)、自制的三嗪类成炭发泡剂(CFA)等复配制成膨胀型阻燃剂(IFR),以二氧化硅、二氧化钛等为协效剂阻燃聚丙烯(PP)。研究了不同组分的IFR及协效剂对阻燃PP复合材料阻燃性能、力学性能和耐水性能的影响。结果表明:改性APP的亲水性下降;由改性APP/CFA(4/1)、二氧化硅协效剂复配的PP复合材料阻燃性能、力学性能优良,助剂在PP基体中分散性好,热水浸泡后氧指数为32.5%,仍能达到UL94V—1级,失重率为2.92%。     

膨胀型阻燃剂与包覆红磷协效阻燃EPDM/EVM共混胶的研究

探讨了膨胀型阻燃剂和包覆红磷对EPDM/EVM共混胶的阻燃作用及两者之间的协效阻燃作用。结果表明,阻燃剂APP/PER配比为3∶1时阻燃效果最佳,极限氧指数(LOI)可达25.7;包覆红磷单用时对EPDM/EVM共混胶有一定的阻燃作用,但效果不理想;膨胀型阻燃剂与包覆红磷并用时,存在P—N协效阻燃作用。     

膨胀阻燃体系概述

综述了膨胀型阻燃剂的研究状况及其组成和阻燃机理;指出了在膨胀阻燃聚烯烃中出现的问题,提出了一些改进的方法;同时详细介绍了膨胀型阻燃剂用协效剂;对物理膨胀型阻燃剂的特点进行了综述;并与化学膨胀型阻燃剂进行了比较;最后展望了膨胀型阻燃剂的发展趋势,多功能、环保和三位一体的膨胀型阻燃剂是未来的发展方向。     

水性超薄膨胀型钢结构防火涂料的制备与性能

以丙烯酸乳液为基体树脂,多聚磷酸铵、三聚氰胺和季戊四醇构成的膨胀型阻燃剂和阻燃协效剂为阻燃体系,制备了水性超薄膨胀型钢结构防火涂料,系统考察了防火涂料中阻燃剂和阻燃协效剂的含量对耐火性能的影响,通过正交实验对阻燃剂巾各组分间的配比进行了优化.研究结果表明:多聚磷酸铵、三聚氰胺和季戊四醇按质量比5:3:2进行复配时,所得膨胀型阻燃剂具有最佳的阻燃效果;在内烯酸乳液中添加该阻燃剂35.7%,阻燃协效剂5.1%制得的防火涂料,当涂层厚度为1.0 mm时,耐火时间高达95.3 min,明显高于国标规定的大于60 min的标准;防火涂料中的阻燃协效剂住燃烧时参与炭层的生成,对炭层有增强作用.     

无卤膨胀型阻燃剂研究进展及趋势

从经典膨胀型阻燃体系的协效研究,经典膨胀型阻燃体系的改性研究,聚合物型成炭剂在无卤膨胀型阻燃剂体系中的应用几个方面,论述了无卤膨胀型阻燃剂的研究进展,并提出了无卤膨胀型阻燃剂今后发展中需要关注的问题。     

疏水膨胀型阻燃聚丙烯的制备及与La2O3的协效阻燃

采用四乙氧基硅烷（TEOS）作为改性修饰剂,分别对季戊四醇（PER）和聚磷酸铵（APP）进行表面改性,制备得到膨胀型阻燃剂（IFR）,对改性后的IFR进行了红外光谱及热失重分析等表征,确认了硅的引入;向改性阻燃剂中加入纳米氧化镧（La2O3）作为阻燃协效剂,然后与聚丙烯（PP）混合,制备了疏水性膨胀型阻燃PP;研究了改性前后复合阻燃剂对PP阻燃性能和力学性能的影响。结果表明,改性后的阻燃体系表现出了较好的疏水性能,加入协效剂La2O3后,材料的阻燃性能和力学性能均较改性之前有所提高。     

三邻苯二胺基环三磷腈的合成及在EVA中的阻燃研究

以六氯环三磷腈和邻苯二胺为为起始原料,甲苯为溶剂,三乙胺为缚酸剂,一步法合成三邻苯二胺基环三磷腈(HACTP)。采用HPLC、FT-IR、MS、31P-NMR和1H-NMR对化合物进行了表征。所得HACTP和聚磷酸铵(APP)、阻燃协效剂复配成膨胀型阻燃剂(IFR),添加到EVA材料中进行阻燃研究。通过对不同配方的试验,得到阻燃效果较好的阻燃剂配方:HACTP为32.84%,APP为50.04%,阻燃协效剂为17.12%。用该配方阻燃的EVA,LOI为36.8%,拉伸强度为5.46 MPa,断裂伸长率为594.95%,整体性能优良。     

新型磷-氮膨胀阻燃剂在改性聚丙烯中的应用研究

采用自制干法合成的磷-氮膨胀型阻燃剂(磷酸酯三聚氰胺盐,IFR)复配聚磷酸胺(APP)和聚四氟乙烯(PT-FE)阻燃改性聚丙烯(PP),利用极限氧指数法、垂直燃烧法分析了阻燃PP的燃烧性能,通过热重分析仪、傅里叶变换红外光谱仪、扫描电子显微镜和X射线光电子能谱对阻燃PP的热降解过程、燃烧性能、残炭结构进行了分析,并研究了燃烧过程中复配阻燃体系对PP的阻燃机理。结果发现,IFR、APP和PTFE之间具有明显的阻燃协效作用;当阻燃剂总添加量为24%(APP为6%、IFR为17.5%、PTFE为0.5%)(质量分数)时,阻燃PP的极限氧指数达到30.1%,垂直燃烧测试达UL 94V-0级;加入阻燃剂还能提高PP的热稳定性。     

ABS新型无卤膨胀阻燃体系的研究

以聚磷酸铵(APP)为酸源,聚对苯二甲酰己二胺(PA6T)为炭源,探讨了不同比例的APP/PA6T复配对丙烯腈-苯乙烯-丁二烯共聚物(ABS)燃烧性能及其降解成炭行为的影响。结果表明,当APP含量为25%、PA6T含量为5%时,阻燃体系的极限氧指数达到29%,通过UL-94测试V-1级;再添加2%协效剂次磷酸铝,可通过V-0级。热失重分析表明,PA6T有较好的成炭作用,APP能极大改变PA6T的热分解行为,使ABS/APP/PA6T阻燃体系的高温残炭率大大提高。SEM形貌分析表明,阻燃体系燃烧表面形成了膨胀、均匀、致密的炭层结构。此外,通过对残炭进行红外分析,发现存在化学键P—O—C,进一步验证了该膨胀阻燃体系的协效成炭行为。     

不同聚合度成炭剂在膨胀阻燃聚丙烯中的应用研究

以三聚氯氰、乙胺、乙醇胺和乙二胺为原料,通过控制物料比合成了4种不同聚合度的成炭-发泡剂(CFA)。将合成的CFA与聚磷酸铵(APP)及纳米二氧化硅复配成膨胀阻燃剂并添加到聚丙烯(PP)中,制备阻燃PP材料。通过热重分析、氧指数、垂直燃烧和力学性能测试研究了材料的热稳定性、阻燃性能和力学性能。结果表明:随着CFA聚合度的增加,膨胀阻燃体系对PP材料的阻燃效率相应提高;阻燃剂的加入提高了PP材料的热稳定性,CFA聚合度的变化对阻燃PP材料的力学性能影响不大。当CFA的聚合度为40时,阻燃PP材料的阻燃性能和热稳定性能均达到最佳。     

Synergistic flame retardant effect of piperazine salt and ammonium polyphosphate as intumescent flame retardant system for polypropylene

Amino trimethylene phosphonic acid piperazine (ATPIP) salt, as a novel charring agent, is prepared via a simple ionic reaction in distilled water using amino trimethylene phosphate (ATMP) and piperazine as raw materials. The synergistic flame retardant effect of ATPIP and ammonium polyphosphate (APP) as an intumescent flame retardant (IFR) is investigated by various characterization and testing methods. The results show that the polypropylene (PP)/modified APP with piperazine (MAPP)/ATPIP ternary blend passes UL-94 V-0 rating and achieve a limiting oxygen index (LOI) of 30% at a loading level of 25 wt% IFR (MAPP:ATPIP = 3:1). Meanwhile, the total smoke production (TSP) value of IFR-PP samples is 3.3 m², which decreases by 93.2% compared with that of pure PP, exhibiting excellent smoke suppression performance. Besides, the analysis of gaseous pyrolysis products and char residue indicates that the IFR-PP samples show a synergistic flame-retardant mechanism including the gas phase and the condensed phase.     

Synergistic Effect of Montmorillonite and Intumescent Flame Retardant on Flame Retardance Enhancement of ABS

The synergistic effects of organic montmorillonite (OMMT) and intumescent flame retardant (IFR) based on the ammonium polyphosphate (APP) and pentaerythritol (PER) on flame retardant enhancement of acrylonitrile-butadiene-styrene copolymer (ABS) were investigated by using the limiting oxygen index (LOI), the UL-94 (vertical flame) test, thermogravimetric analysis (TGA), x-ray diffractometry (XRD) and scanning electron microscopy (SEM). The LOI data and vertical flame tests show that OMMT has a synergistic flame retardant effect with IFR and the LOI value of ABS/OMMT/IFR (96/4/20) reaches 28.7%. The TGA data demonstrate that the incorporation of OMMT and IFR is very effective in enhancing the thermal stability of ABS/OMMT/IFR system at high temperature (T > 500°C). The results of XRD show that the composite of ABS/OMMT is a kind of intercalated nanocomposite and the gallery height of ABS/OMMT nanocomposite is 3.5 nm. The microstructures observed by SEM demonstrate that a suitable amount of OMMT with IFR can promote formation of compact intumescent charred layers in ABS blends.     

无卤膨胀阻燃剂在低密度聚乙烯中的应用研究

以干法合成的P-N无卤膨胀阻燃剂(IFR)为基础,配合聚磷酸胺(APP)并且将金属氧化物(ZnO)作为协效剂阻燃改性低密度聚乙烯(PE-LD)。采用扫描电子显微镜对该体系燃烧后的炭层结构进行了分析。通过红外光谱和X射线光电子能谱研究了该体系在不同温度热处理后的残炭组成,并分析了该膨胀型阻燃体系对PE-LD的阻燃机理。结果表明,PE-LD/IFR/APP/ZnO体系的极限氧指数可以达到27.9%,垂直燃烧性能达到UL 94V-0级。     

Intumescent flame retardant for polymers. III. The polypropylene–ammonium polyphosphate–polyurethane system

The action of some mixtures of ammonium polyphosphate (APP) and polyurethanes (PUr) as flame retardant (FR) agents for polypropylene (PP) was examined. The APP–PUr systems behave as intumescent flame retardant (IFR) formulations. The IFR action of these systems is described by the comparison of the oxygen index (OI) values measured on molded pellets and on molded rods, by measurements of the polymer temperature just below the burning surface and by visual observations. A strong synergism between APP and some polyurethanes, having piperazine units in the polymer chain, was ascertained with a maximum 3:1 ratio. Our results also indicate that only polyurethanes with specific structure, in combination with APP, are active as IFR agents on PP combustion.     

Synergistic effect of a novel charring agent with ammonium polyphosphate on flame retardancy and thermal degradation of acrylonitrile‐butadiene‐styrene copolymer

A novel charring agent poly(1,3‐propylene terephthalamide) (PPTA) was synthesized and characterized by Fourier transform infrared spectroscopy and ¹H nuclear magnetic resonance. This novel charring agent combined with ammonium polyphosphate (APP) was adopted as an intumescent flame retardant (IFR) to impart flame retardance and dripping resistance to acrylonitrile‐butadiene‐styrene copolymer (ABS). Flammability and thermal behaviors of the treated ABS were investigated by limiting oxygen index, vertical burning test and thermogravimetric analysis. The results showed that the IFR with the novel charring agent had both excellent flame retardant and anti‐dripping abilities for ABS. The thermogravimetric analysis curves indicated that there was a synergistic effect between PPTA and APP, which greatly promoted the char formation of IFR‐ABS composites. Meanwhile, the thermal degradation mechanism of PPTA and APP/PPTA was characterized using thermogravimetric analysis/infrared spectrometry. The results demonstrated that APP changed the thermal degradation behavior of PPTA and reacted with PPTA to form a crosslinked structure. Additionally, the structure and morphology of char residues were studied by Fourier transform infrared spectroscopy and scanning electron microscopy. Copyright © 2011 Society of Chemical Industry     

用反相悬浮聚合法制备膨胀型阻燃剂及其在丁苯橡胶中的应用

采用反相悬浮法聚合丙烯酸钠,同时将化学膨胀阻燃体系(IFR)三组分聚磷酸铵、季戊四醇和三聚氰胺加入到聚合体系中进行原位包裹,用傅里叶变换红外光谱对聚合产物的结构进行了表征,研究了三聚氰胺用量和聚磷酸铵与季戊四醇配比对丁苯橡胶硫化胶阻燃效果的影响,采用热重法分析了阻燃丁苯橡胶的热性能,并通过扫描电镜观察了添加IFR的丁苯橡胶在燃烧后表面的微观形态。结果表明,三聚氰胺的质量分数为IFR体系的3.0%、聚磷酸铵与季戊四醇的质量比为4.00～5.67时IFR体系的剩炭率最高,阻燃性能较好;添加IFR后丁苯橡胶的阻燃性能得到相应改善,当IFR质量分数为30%时丁苯橡胶硫化胶的极限氧指数可达27.5%;添加了IFR的丁苯橡胶硫化胶在燃烧时形成了较为致密的泡沫炭层,表明IFR对丁苯橡胶具有较好的膨胀阻燃效果。