Improvement of flame retardancy in phenolics and paper-sludge/phenolic composites

Paper-sludge/phenolic composites were fabricated using a novolac-type phenolic resin and paper sludge. A phosphate flame retardant containing halogen (tris 2-chloroethyl phosphate) and inorganic flame retardant (aluminum trihydroxide) were introduced into neat phenolics and paper-sludge/phenolic composite in order to improve their flame retardancy. In addition, magnesium hydroxide and halogenated flame retardant were added into the paper-sludge/phenolic composite. The flame retardancies were estimated with the UL 94 test. To study the flame retardant mechanism, thermal analysis of the phenolics and the paper-sludge/phenolic composites were carried out using a thermogravimetric analyzer and a differential scanning calorimeter. The phosphated flame retardant and inorganic flame retardant both showed the flame retardant effect on the phenolics. However, the flame retardancy of the paper-sludge/phenolic composite was enhanced only by phosphated and halogenated flame retardants. This result is attributed to the fact that the flame retardancies of the phenolics and paper-sludge/phenolic composite depend on their heat capacities and decomposition behaviors. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2043–2050, 1998     

ABS树脂添加型阻燃的研究进展

ABS阻燃技术主要包括：添加型阻燃体系、反应型阻燃体系、难燃聚物混合体系,添加型阻燃体系被广范的应用于ABS树脂阻燃领域。本文对ABS树脂添加型阻燃体系所包括卤化阻燃体系和非卤化阻燃体系进行了介绍,并阐述了不同阻燃体系的优势及所存在的问题,对不同阻燃体系的发展进行了展望。     

阻燃LDPE的研究

主要研究了添加卤素阻燃剂如氯化石蜡（CP）、双（六氯环在戊二烯）环辛烷（DCRP）和十溴联苯醚（DBDPO）的低密度聚乙烯（LDPE）燃烧性．用锥形量热仪和极限氧指数实验测试了其燃烧特性，讨论了卤素阻燃剂对LDPE力学性能的影响。结果表明．与纯LDPE相比．添加了卤素阻燃剂的LDPE的热释放速率峰值（QPHKR）、质量损失速率（QMLR）显著降低，但生烟速率（QSPR）增大；加入DCRP的LDPE的质量热释放速率（QHRR）、质量损失（QML）低于其他2种阻燃体系的，加入DBDPO的LDPEQHKR最高．添加CP的LDPEQSPR最低；并用卤素阻燃剂和Sb2O3后，LDPE的阻燃效果更为显著；DCRP对LDPE的拉伸强度影响最大，DBDPO对LDPE的断裂伸长率影响最小；DCRP，DBDPO．CP的加入提高了LDPE的弯曲强度。     

缩合磷酸胍阻燃浸渍绝缘纸的应用研究

纸及纸制品的阻燃是阻燃研究的重要领域之一，本文利用自己研制的缩合磷酸胍为阻燃剂研究了对浸渍绝缘纸的阻燃性能以及对其它性能的影响。通过与国家标准进行比较结果表明，该阻燃剂对浸渍绝缘纸进行阻燃处理后，不仅能获得良好的阻燃性能，而且对浸渍绝缘纸的其它性能影响小，并符合国家标准。     

Flame retardant epoxy resin for electrical and electronic applications

Amine‐cured epoxy resins were prepared at 2% by weight phosphorus content using four halogen‐free flame retardants; poly(m‐phenylene methyl phosphonate) (Fyrol PMP); 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide; red phosphorus; and aluminum diethylphosphinate (OP1230). The effect of these additives on the properties of cured epoxy, including glass transition temperature, thermal stability, and fire retardancy (cone calorimetry), were studied and were compared with the conventionally used flame retardant, tetrabromobisphenol‐A (TBBA). All properties are improved for the non‐halogenated materials compared with TBBA. Further, the stoichiometric amounts of Fyrol PMP and TBBA (without an external curing agent) were reacted with epoxy to determine if they could be used as a flame retardant and as a curing agent; Fyrol PMP effectively acts as a flame retardant and as a curing agent. Evolved gas analysis is also discussed through thermogravimetric analysis/Fourier transform infrared spectroscopy. Copyright © 2013 John Wiley & Sons, Ltd.     

苯乙烯系阻燃塑料合金的研究进展

综述了国内外近年来在苯乙烯系阻燃塑料合金方面的研究进展。主要介绍了高聚物型卤系阻燃剂、磷系阻燃剂、有机硅系阻燃剂的特性及其在提高苯乙烯系塑料合金阻燃性能方面的应用。与目前常用的低分子卤系阻燃剂相比，这些阻燃剂对环境污染小，对塑料基材的机械性能和加工性能损害程度少。此外，还简要介绍了纳米复合技术在提高苯乙烯系塑料阻燃性能中的应用。     

低烟低卤阻燃PVC预分支电缆专用料的研制

研究了1种金属氧化物固溶体与氢氧化铝（ATH）的共混物对聚氯乙烯（PVC）预分支电缆专用料的阻燃性、消烟性、物理机械性能、成型加工性、热稳定性以及HCl释放量的影响。结果表明，该共混物对PVL、具有高效的阻燃、消烟、降卤作用，2份金属氧化物固溶体代替2份氧化锑可达到同样的阻燃消烟降卤效果，且综合性能优良．价格低廉。     

The Effect of Selected Phosphates on the Flame Retardancy of Cotton and Polyester Fabrics

The comparative effects of three selected phosphates on the flame retardancy of pure cotton and polyester fabrics have been chosen from the author's previous investigations. Earlier described procedure for the evaluation of flame retardancy were used. The optimum loading required to achieve flame retardancy indicated the inferiority of sodium polymetaphosphate as compared with the others.     

聚乙烯无卤阻燃剂TE—3的开发应用

考察了红磷与常用阻燃剂的协同效果,确定了无卤阻燃剂ＴＥ－３的组成,将其用于ＰＥ电缆料,达到了预期的燃效果。     

Synergistic effect of organophosphate functionalized montmorillonite on properties and water resistance of intumescent flame‐retarded SEBS

Polystyrene‐b‐(ethylene‐co‐butylene)‐b‐styrene (SEBS) is a widely used thermoplastic elastomer. However, it suffers from poor flame retardancy. Proper combination of organic‐modified montmorillonite and intumescent flame retardant (IFR) works but is not stable due to easy absorption of moisture. In this study, a novel and stable halogen‐free flame‐retardant system is demonstrated by encapsulating a hydrophobic organophosphate, ie, bisphenol A bis (diphenyl phosphate) (BDP) into a stable micelle and then “attaching” the BDP micelles to the montmorillonite (called: side‐intercalation). The resulted BDP modified montmorillonite (BMMT) has a large inter‐platelet spacing and demonstrated synergistic effect with IFR on flame retardancy, tensile property, and water resistance for the composite with SEBS. In addition to more homogeneous dispersion of IFR and BMMT, a longer‐lasting interfacial interaction between IFR and SEBS matrix with addition of small amount of BMMT also plays the role. The results suggest that BMMT can serve as an effective additive for formulating novel halogen‐free flame retardants for the SEBS to meet increasingly stricter environmental requirements.     

无卤协效膨胀阻燃聚甲醛体系的性能和阻燃机理

针对聚甲醛(POM)难以阻燃的难题,采用酚醛树脂协效无卤膨胀阻燃剂复合阻燃POM,研究了酚醛树脂含量对POM阻燃性能和力学性能的影响以及相关的成炭阻燃机理.结果表明,酚醛树脂的含量对无卤膨胀阻燃POM体系的阻燃性能有重要影响,当体系中酚醛树脂的质量分数为0.5%～2.0%时,相应阻燃POM体系可达UL941.6 mm ...     

Flame retardancy in fabric consisting of cellulosic fiber and modacrylic fiber containing fine‐grained MoO3 particles

Flame retardancy of fabrics consisting of modacrylic fiber containing with various dispersed metal compounds and cellulosic fiber has been investigated by means of flame test (ISO15025 procedure A) and limiting oxygen index (LOI). It has been found that excellent flame retardancy is achieved by fine‐grained MoO₃ particles. The afterflame time in flame test and the LOI value are improved with decreasing particle size of MoO₃. The flame retardancy of MoO₃ (particle size; 0.1 µm) is comparable to that of Sb₂O₃. On the other hand, significant improvement in flame retardancy is not observed for other metal compounds although some metal oxides and a hydroxide in the present study are known as flame retardant or smoke suppressing agent in halogen containing polymer in previous studies. In order to clarify the mechanism of the observed flame retardancy by the addition of fine‐grained MoO₃, we have carried out X‐ray fluorescence spectrometry (XRF) measurement of the fabric specimen after the flame test and thermogravimetric analysis (TGA) of various types of samples. These analytical data indicated that MoO₃ works as halogen synergist in solid phase and the char of modacrylic fiber formed by addition of MoO₃ suppresses decomposition of the cotton blended in the fabric in the range of the ignition temperature. Copyright © 2015 John Wiley & Sons, Ltd.     

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.     

阻燃硅氧聚氨酯

含硅氧基团的聚氨酯是一种本质阻燃高聚物,它在受强热和暴露于火中时,表面可形成连续的、抗氧化的硅酸盐保护层而具有优良的阻燃作用。当在这类聚氨酯中引入卤素时（如合成时以合溴多元醇为扩链剂）,则阻燃效果尤佳。本文综述了硅氧聚氨酯的特性、合成路线及阻燃性能。     

Flame retardant polyesters based on bromine derivatives

Unsaturated polyesters containing halogens in the backbone of the polymer chain were synthesized. Derivatives used had brominated functional groups such as tetrabromobisphenol A, tetrabromophthalic anhydride, and dibromoneopentyl glycol. These were compared to chlorine-containing polyesters based on HET acid and tetrachlorophthalic anhydride and an additive exhibiting a synergistic effect of phosphorus and halogen, trichloroethyl phosphate. Optical properties before and after artificial weathering (up to 1650 hr), were determined on cast specimens, and mechanical properties (flexural strength, modulus, and hardness) and flame retardancy were determined on glass fiber laminates. The flammability tests consisted of the “oxygen index” and the “self-extinguishing time” tests, which were correlated for various halogen concentrations and different compositions. The efficiency of bromine in flame retardancy has been found to be much higher than that of chlorine. The minimal concentration of bromine required for self-extinguishing is 10–12%, as compared with 20–25% for chlorine. A general performance index for polyesters has been derived which incorporates both flame and weather resistivity factors of the modified polyesters.     

聚硼硅氧烷阻燃剂的合成工艺及其在聚碳酸酯中的应用

采用二步合成法制备了聚硼硅氧烷阻燃剂(PB),通过改变硼酸/硅烷比、缩合温度、水解时间优化了PB的合成工艺。同时研究了PB对聚碳酸酯(PC)阻燃性能和物理性能的影响。结果表明:严格控制硼酸/硅烷比和缩合温度是制备高效阻燃PB的关键,当硼酸/硅烷比(摩尔比)为1:1、缩合温度为100℃时所制备的PB的阻燃性能最好,在PC中添加5%(质量分数)该PB阻燃剂,PC的极限氧指数(LOI)从26%提高到39.4%。在热降解过程中,PB使PC的起始降解温度降低,但可使PC的热降解速率降低,高温残炭量增加,从而提高了PC的阻燃性能。添加PB可以基本保持PC优良的力学性能。另外,PB可保持PC原有的透明性,PC/PB阻燃材料仍旧呈透明状态。     

Flame retardancy and thermal properties of organoclay and phosphorous compound synergistically modified epoxy resin

Phosphorous flame retardants (PFRs) are common halogen‐free flame retardants. However, the flame retardancy of PFRs has not been fully exploited. Herein, the synergistic flame retardant effect of a typical phosphorous compound, 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO), and organoclay on epoxy is studied. Results show that the peak of heat release rate (pHRR) and smoke production rate of modified epoxy resin (EP) with both 2.0 wt % phosphorus and 4.0 wt % organoclay are only 40% and 46% of that of neat EP resin, respectively, while the sole use of 2.0 wt % phosphorus only decrease the pHRR to 59% of that of neat EP resin. The structure and thermal decomposition behavior of as‐prepared nanocomposites are analyzed, and a synergistic flame retardant mechanism is proposed. This investigation opens a new approach to obtain halogen‐free EPs with higher flame retardancy and better overall properties than the EPs loaded with DOPO only. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43367.     

Investigation on phosphorus halogen‐free flame‐retardancy systems in short glass fiber‐reinforced PC/ABS composites under rapid thermal cycle molding process condition

In this study, standard test specimens with flame‐retarded short glass fiber‐reinforced PC/ABS materials were fabricated under rapid thermal cycle injection molding condition by selecting a potassium perfluorobutane sulfonate flame retardant specially used for PC, FR2025, and two kinds of aryl phosphorus halogen‐free flame retardants, UN707 and PX‐220. The flame‐retardancy effect of the above different flame retardants on the studied systems was compared through combustion tests of the specimens. Meanwhile, the thermal and mechanical properties of flame‐retarded composites were studied by using the thermogravimetry analysis, dynamic mechanical thermal analysis (DMTA), and universal testing machine. The results show that the “candlewick effect” of fibers exacerbates the fire behavior of composites. With the increase of the aryl phosphorus halogen‐free flame retardants, the flame‐retardancy effect of composites is obviously improved, and the maximum thermal degradation rate of composites is significantly decreased. The UL94 combustion rating is improved, and the time of residual flame is substantially reduced with the increase of PC content under the same content of flame retardant. The DMTA results show that the flame retardants have a reinforcement action on PC/ABS matrix. However, the macroscopic mechanical properties are slightly decreased in the glass fiber‐reinforced composites because of the destructive effect of the flame retardants on the interface compatibility between matrix and fibers; the scanning electron microscopic micrographs of tensile fracture fully prove this action mechanism of flame retardants. In addition, the addition of toughener and antidripping additive significantly affects the flame retardancy and mechanical properties of composites. POLYM. COMPOS., 36:1653–1663, 2015. © 2014 Society of Plastics Engineers     

Flame retardancy of thermoplastic polyesters—a review of the recent literature

An overview is presented of the literature on the flame retardancy of thermoplastic polyesters, especially poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT). The main focus is on publications of the last fifteen years; however, some earlier work of major importance is discussed as well. Because PET and PBT almost totally convert to volatile fragments upon exposure to heat, providing fuel to the flame, it is a challenging task to flame‐retard these polymers. Although many of the commercially available systems for flame retardancy of PET and PBT consist of a halogen‐containing additive and a synergist, more recent publications and patents emphasize halogen‐free, particularly phosphorus‐based systems. Several phosphorus‐based additive or reactive systems are well‐established for use in PET textiles, and phosphorus‐based additives have recently been introduced for PBT. Copyright © 2004 Society of Chemical Industry     

阻燃改性双马来酰亚胺树脂的研究进展

介绍近年来对双马来酰亚胺（BMI）树脂阻燃的最新研究进展,包括卤系阻燃剂、磷系阻燃剂、氮系阻燃剂、硅系阻燃剂、硼系阻燃剂、锑系阻燃剂和铝一镁系阻燃剂等的阻燃机理和应用状况一指出,在不损失树脂物理、力学等性能的前提下采用无卤阻燃将是今后的发展方向。