Zinc hydroxystannate and zinc stannate as flame‐retardant agents for flexible poly(vinyl chloride)

The flame‐retardant and smoke‐suppressant properties of inorganic tin compounds such as zinc hydroxystannate (ZHS) and zinc stannate (ZS) were investigated in a comparison with alumina trihydrate, magnesium hydroxide, and Sb₂O₃ through the limiting oxygen index test and smoke density test. The flame‐retardant mechanisms were studied through the char yield test, SEM, quantitative analysis, thermogravimetry and differential thermal analysis. The thermal degradation in air of flexible PVC treated with the above compounds was studied by thermal analysis from ambient temperature to 800°C. The results showed that tin compounds such as ZHS and ZS could be used as a highly effective flame retardant for flexible PVC, and it appears that the tin compound may exert its action in both the condensed and vapor phases, but mainly in condensed phases as a Lewis acid. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1469–1475, 2005     

系列羟基锡酸盐对半硬质PVC的阻燃消烟作用

研究了系列羟基锡酸盐阻燃剂对半硬质PVC的阻燃消烟作用。通过对样品燃烧后剩炭含量及扫描电镜(SEM)分析,探讨了锡酸盐体系阻燃抑烟的机理。结果表明:经阻燃处理的样品具有较高的极限氧指数(LOI)和剩炭率,较低的烟密度等级(SDR)和最大烟密度(MSD),与未处理的样品相比具有较好的阻燃和消烟性能。由于阻燃剂的添加量较少,对材料力学性能影响不大。     

氧化锌和氢氧化物对软聚氯乙烯阻燃性能的影响

引言 软质PVC制品中由于大量增塑剂的加入,大大提高了其可燃性,燃烧时还会产生大量有毒烟雾,因此对PVC制品的阻燃抑烟问题亟待解决.无机氢氧化物优点众多,在阻燃高分子材料中应用广泛,但阻燃效率低,常与其他阻燃剂复配使用.硼酸锌、锡酸锌、磷酸锌、氧化锌等可直接或与其他阻燃剂复合应用于PVC的阻燃消烟[1-3].     

羟基锡酸锌包覆纳米氢氧化镁在PVC中的应用

通过均匀沉淀法制备了羟基锡酸锌包覆纳米氢氧化镁并将其应用到聚氯乙烯(PVC)中。利用XRD、TG、DTA对羟基锡酸锌包覆纳米氢氧化镁的性能进行了研究,并通过氧指数、烟密度研究了羟基锡酸锌包覆纳米氢氧化镁对PVC的阻燃和抑烟性能的影响,同时对其力学性能也进行了研究。结果表明:纳米氢氧化镁表面均匀地包覆了羟基锡酸锌;羟基锡酸锌包覆纳米氢氧化镁对PVC的阻燃和抑烟性能明显优于单独添加羟基锡酸锌、纳米氢氧化镁以及羟基锡酸锌包覆微米氢氧化镁和羟基锡酸锌与纳米氢氧化镁混和物时的阻燃、抑烟性能;纳米材料的加入对PVC的力学性能也产生了有利的影响。     

Synergistic flame retardant effects of activated carbon and molybdenum oxide in poly(vinyl chloride)

The synergistic effects of activated carbon (AC) and molybdenum oxide (MoO₃) in improving the flame retardancy of poly(vinyl chloride) (PVC) were investigated. The effects of AC, MoO₃ and their mixture with a mass ratio of 1:1 on the flame retardancy and smoke suppression properties of PVC were studied using the limiting oxygen index and cone calorimeter tests. It was found that the flame retardancy of the relatively cheaper AC was slightly weaker than that of MoO₃. In addition, the incorporation of AC and MoO₃ greatly reduced the total heat release and improved smoke suppressant property of PVC composites. When the total content of AC and MoO₃ was 10 phr, PVC/AC/MoO₃ had the lowest peak heat release rate and peak smoke production rate values of 173.80 kW m^?2 and 0.1472 m² s^?1, which represented reductions of 47.3 and 59.9%, respectively, compared with those of PVC. Furthermore, thermogravimetric analysis and gel content tests were used to analyze the flame retardant mechanism of AC and MoO₃, with results showing that AC could promote early crosslinking in PVC. Char residue left after heating at 500 °C was analyzed using scanning electron microscopy and Raman spectroscopy, and the results showed that MoO₃ produced the most compact char, with the smallest and most organized carbonaceous microstructures. © 2017 Society of Chemical Industry     

Tin dioxide coated calcium carbonate as flame retardant for semirigid poly(vinyl chloride)

The flame retardant and smoke suppressant properties of semirigid PVC treated with calcium carbonate (CaCO₃), tin oxide (SnO₂), the mixture of CaCO₃/SnO₂ and SnO₂‐coated CaCO₃ have been studied through the limiting oxygen index, char yield, and smoke density rating (SDR) methods. The thermal degradation in air of the treated semirigid PVC was studied by thermogravimetry (TG) and differential thermal analysis (DTA) from ambient temperature to 1073 K. The morphologies of the additives and the char formation were studied through SEM. The mechanical property was also studied. The results showed that the semirigid PVC treated with SnO₂‐coated CaCO₃ has a higher limiting oxygen index and char yield, lower SDR and MSDR, a more compact structure of char formation than the semirigid PVC without flame retardant and the semirigid PVC with the equivalent CaCO₃, or SnO₂, or the mixture of CaCO₃/SnO₂, a similar tensile property and greatly improved impact strength compared with that of the semirigid PVC without flame retardant. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 731–738, 2006     

Flame retardant flexible poly(vinyl chloride) compound for cable application

ZnO/MgO, ZnO/CaO, and ZnO/CaO/MgO can form solid solutions. The solid solution for we as flame retardant (SSFR) was obtained by annealing at 1023 K for 4.5 h in a muffle furnace. Flexible poly (vinyl chloride) (PVC) filled with SSFR and Sb₂O₃ was investigated by differential thermal analysis thermogravimetry. Limiting oxygen index (LOI), mechanical properties, and electrical properties were studied. The surface of the char formed after combusting of the PVC compounds was observed through scanning electron microscopy and the effect of the surface area to the LOI was also studied. The data suggested that a small amount of SSFR and Sb₂O₃ have good synergy and can greatly increase the LOI and the char yield, and that the thermal degradation temperature and the activation energy decreased. It can be concluded that the mechanism of SSFR is a condensed‐phase mechanism. Moreover, one can conclude that the surface area can enhance the LOI. All the results showed that SSFR is effective and safe as a flame retardant in flexible PVC. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3137–3142, 2003     

软质聚氯乙烯用阻燃剂

主要综述了软质聚氯乙烯常用的阻燃剂体系，重点介绍了阻燃增塑剂、金属化合物阻燃剂、无机物单质阻燃剂、无机填料阻燃剂、含卤聚合物阻燃剂以及有机化合物阻燃剂在软质聚氯乙烯中的使用情况。     

硼酸锌在聚丙烯(PP)中阻燃效果的研究

本文研究了硼酸锌分别在有卤和无卤阻燃PP材料中协同作用,对不同添加量的阻燃聚丙烯进行物理机械性能及阻燃性能的检测分析,结果表明:硼酸锌的加入可明显提高PP的阻燃性能:在含卤阻燃PP材料中添加硼酸锌,可有效改善阻燃体系的抑烟性,在无卤阻燃PP体系中可显著提高材料的阻燃性,降低阻燃剂的使用量,改善材料的力学性能。     

阻燃抑烟剂锡酸锌和羟基锡酸锌的研究进展

简要介绍了阻燃抑烟剂锡酸锌和羟基锡酸锌的性质,综述了它们的制备方法、应用范围及阻燃和抑烟机理的研究进展.作为两种无毒绿色阻燃抑烟剂,它们有很好的发展前景.最后对它们的研究与开发提出了建议.     

Flame‐retardant properties of magnesium hydroxystannate and strontium hydroxystannate coated calcium carbonate on soft poly(vinyl chloride)

The flame‐retardant and smoke‐suppressant properties of soft poly(vinyl chloride) (PVC) treated with zinc hydroxystannate (ZHS), calcium carbonate (CaCO₃), magnesium hydroxystannate [MgSn(OH)₆], strontium hydroxystannate [SrSn(OH)₆], ZHS–MgSn(OH)₆, ZHS–SrSn(OH)₆, MgSn(OH)₆‐coated CaCO₃, SrSn(OH)₆‐coated CaCO₃, ZHS–MgSn(OH)₆‐coated CaCO₃, and ZHS–SrSn(OH)₆‐coated CaCO₃ were studied with the limited oxygen index, char yield, and smoke density rating methods; the mechanical properties were also studied. The results showed that, with the equivalent addition of the corresponding hydroxystannate, the soft PVC treated with hydroxystannate‐coated CaCO₃ had a higher limited oxygen index than the corresponding hydroxystannate, and the soft PVC treated with the agents containing magnesium had a higher limited oxygen index than the soft PVC treated with the agents containing strontium, except for ZHS–MgSn(OH)₆‐coated CaCO₃. The improvement in the char formation of the hydroxystannate‐coated CaCO₃ was better than that of the corresponding hydroxystannate in most cases, and the aforementioned agents reduced the smoke density rating, decreased the tensile strength, and increased the elongation and impact strength basically. Thermal analysis showed that the additives promoted the evolution of hydrogen chloride, early crosslinking, and rapid charring through the strong catalyzing effect of Lewis acids. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

阻燃抑烟剂对软聚氯乙烯材料燃烧性能的影响

针对氢氧化镁、硼酸锌、三氧化二锑等常用的阻燃抑烟剂对在软聚氯乙烯燃烧时的热释放速率和一氧化碳释放量进行了研究 ,发现氢氧化镁和硼酸锌虽然可以降低材料的热释放性能和发烟量 ,但是会大大增加烟气中一氧化碳的释放量 ;而三氧化二锑会增加材料的发烟量 ,但却能大大降低烟气中的一氧化碳的释放量     

无机阻燃剂对PVC/木粉复合材料性能的影响

分别采用A1(OH)3、ZB以及Sb2O3等无机阻燃剂对PVC/木粉复合材料改性,研究不同的阻燃剂配方及阻燃剂含量对PVC/木粉复合材料阻燃性能和力学性能的影响。结果表明:随着A1(OH)3,ZB以及Sb2O3添加量的增加,PVC/木粉复合材料的氧指数(LOI)呈逐渐增大的趋势。Sb2O3阻燃效率最高,当添加量为9份时,氧指数达到35.2%;无机阻燃剂的加入普遍降低了PVC/木粉复合材料的冲击韧性,但对拉伸强度起到了一定的增强作用。     

羟基锡酸锌包覆硫酸钡的制备以及在软PVC中的阻燃应用

通过均匀沉淀法制备了羟基锡酸锌包覆硫酸钡(ZHSCB)样品,并与硫酸钡(BaSO4)对比应用于软PVC的阻燃消烟处理。利用X-射线衍射(XRD)及扫描电子显微镜(SEM)等手段对ZHSCB进行了表征,并通过极限氧指数(LOI)和烟密度等级(SDR测试)研究了ZHSCB对PVC的阻燃消烟作用。通过热分析的方法研究了阻燃PVC从室温到800℃的热降解过程。通过拉伸强度和断裂伸长率测定了ZHSCB对PVC的力学性能的影响。结果表明:ZHSCB对PVC有优异的阻燃消烟作用,能够有效促进PVC第一降解阶段的脱HCl反应,促进交联成炭反应的进行以及剩炭稳定性的提高,并且对于PVC的力学性能影响较小。     

两种形貌的羟基锡酸锌对聚氯乙烯的阻燃作用

以硫酸锌和锡酸钠为原料,制备了不同粒径尺寸的无定形羟基锡酸锌（ZHS）和球形ZHS;对比研究了上述2种ZHS对聚氯乙烯（PVC）的阻燃、消烟、拉伸和降解性能的影响及这2种ZHS在PVC基体中的分散情况。结果表明,当ZHS的添加量相同时,球形ZHS对PVC的阻燃、消烟和拉伸性能的有益影响优于无定形ZHS;ZHS能提高PVC的残炭率,降低其起始分解温度（T1 %）和第一阶段的最大失重峰温度（TM1）,且无定形ZHS比球形ZHS对T1 %和TM1的降低效果更明显;无定形ZHS在PVC基体中的分散性及与PVC基体结合的紧密性都优于球形ZHS。     

无机锡化物阻燃聚氯乙烯研究进展

综述了近几年无机锡化物阻燃软质聚氯乙烯（PVC）的研究现状,介绍了无机锡化物阻燃剂的阻燃机理,并展望了无机锡化物阻燃剂未来的发展趋势和研究方向。     

Bio‐based Mg(OH)2@M‐Phyt: improving the flame‐retardant and mechanical properties of flexible poly(vinyl chloride)

Two novelty bio‐based multifunctional metallic phytate coated (M‐Phyt, M ≡ Cu, Zn) Mg(OH)₂ (MH@M‐Phyt) were designed and incorporated into flexible poly(vinyl chloride) (PVC). MH@M‐Phyt was incorporated into PVC materials in a powder form. The morphology of the interface between MH and M‐Phyt and their binding states were characterized by TEM and X‐ray photoelectron spectroscopy (XPS), respectively. The TEM images of MH@M‐Phyt indicated that M‐Phyt was successfully coated on the MH surface. Additionally, from the XPS spectra M‐Phyt and MH were connected by Mg–O–P bonds. The flame retardancy and mechanical properties of the PVC composites were investigated through the limiting oxygen index, cone calorimetry and mechanical tests. The char residues were analyzed by SEM. The results revealed that the MH@M‐Phyt powder functioned well in PVC, with a flame retardancy, smoke density, tensile strength and elongation at break better than those of PVC/MH. With 10 phr loading, the peak heat release rate of PVC/MH@Zn‐Phyt and PVC/MH@Cu‐Phyt decreased by 33.5% and 24.6%, respectively, benefitting from the formation of firmer and denser char layers on the char residues. © 2019 Society of Chemical Industry     

非晶锡酸锌包覆黏土的制备及阻燃应用

通过直接沉淀法制备了羟基锡酸锌（ZHS）和羟基锡酸锌包覆黏土（ZHS/clay）,经煅烧得到锡酸锌（ZS）和锡酸锌包覆黏土（ZS/clay）。采用X射线衍射（XRD）、扫描电镜（SEM）对产品结构进行表征。实验表明,常温反应4 h制得的ZHS产率较高、晶粒尺寸较规整,ZHS经煅烧制得的ZS为非晶结构,最终包覆产物ZS/clay的包覆形貌清晰。将ZS/clay作为三氧化二锑替代品,应用于十溴二苯乙烷（DBDPE）、三氧化二锑协同阻燃聚丙烯（PP）体系中,当替代50%三氧化二锑时,复合材料垂直燃烧等级可达V-0级,氧指数为23.3%,抗冲击强度为13.18 kJ/m2,接近未使用替代品数据。     

Synthesis,characteristic of a novel flame retardant containing phosphorus and its application in poly(ethylene‐co‐vinyl acetate)

A novel flame retardant (SPDH) containing phosphorus was synthesized through the reaction of 10‐(2, 5‐dihydroxyphenyl)‐9, 10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO‐HQ) and synthesized intermediate product 3, 9‐dichloro‐2, 4, 8, 10‐tetraoxa‐3, 9‐diphosphaspiro(5.5)undecane‐3, 9‐dioxide (SPDPC). The structure and properties of SPDPC and SPDH were characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR) spectroscopy and thermogravimetric analysis (TGA). After blending with poly(ethylene‐co‐vinyl acetate) (EVA), the flame‐retardant properties of EVA/SPDH composites were estimated by cone calorimeter, limited oxygen index (LOI) and UL‐94 tests, whereas the thermal stabilities were investigated using TGA. The morphological microstructure of the char formed by EVA/SPDH composite after combustion in cone calorimeter was investigated by scanning electron microscopy (SEM). The results indicate that the flame retardant and thermal stability were improved by incorporation of SPDH. The rich foamy char layers were observed from the residues after combustion in a cone calorimeter, which exactly benefits the improvement of thermal stability and flame retardant property of materials. Copyright © 2010 John Wiley & Sons, Ltd.