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。     

Influence of PEPA-containing polyether structure on fire protection of transparent fire-resistant coatings

Three kinds of novel PEPA-containing polyether flame retardants were synthesized by 1-oxo-4-hydroxymethyl-2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane (PEPA), phosphorus oxychloride (POCl₃), and polyether with different structures (PEG, PPG, and PTMG). Their structures were confirmed by ¹H nuclear magnetic resonance (¹H NMR) and Fourier transform infrared spectroscopy (FTIR). The solubility test showed that PEPA modified by polyethylene glycol (PEG) and polypropylene glycol (PPG) had better water solubility than that modified by poly(tetrahydrofuran) (PTMG). The decomposition process of PEPA-containing polyether flame retardants (PCPE) was studied by thermogravimetric analysis (TG) and derivative thermogravimetry. A possible mechanism was proposed to analyze the influence of polyether structure on the thermal degradation process of PCPEs. Afterward, the PEPA-containing polyether flame retardants were mixed with melamine formaldehyde resin to prepare the transparent fire-resistant coatings. The influences of polyether structure on the properties of the coatings were investigated in detail by fire protection test, TG, FTIR, X-ray photoelectron spectroscopy (XPS), and scanning electron microscope. It was found that the fire protection of the coating and foam structure of char layer were significantly improved when the number of carbon atoms in a unit of polyether chain was less. TG results showed that the chain unit of polyether with less carbon atom number could increase the residue weights of the coatings. FTIR and XPS result illustrated that the char layers were mainly composed of aromatic rings and phosphorus oxide, and the antioxidation and char-forming ability of coatings were enhanced effectively with the decrease in the number of carbon atoms in a unit of polyether chain.     

New developments in speciality polymers: polymeric stabilizers

Many new speciality polymers have been developed in the last few years. In this paper polymeric stabilizers (antioxidants, flame retardants and ultraviolet stabilizers) will be discussed. Polymeric antioxidants of the hindered-phenol type, copolymers of 2,6-ditertiarybutyl-4-vinyl(or isopropenyl)phenol with styrene, methyl methacrylate, or more importantly butadiene or isoprene have been prepared; hydrogenation of the latter copolymers gave copolymers of the two polymerizable phenolic antioxidants with ethylene or ethylene/propylene. The polymeric antioxidants have been blended with diene polymers and selected polyolefins and have improved the long-term oxidative stability of these polymers. Polymeric flame retardants have been prepared by copolymerizing styrene and/or acrylonitrile with acrylates and methacrylates of aliphatic bromine-containing alcohols or bromine-containing phenols. Polymers with polymer-bound flame retardants have a higher limiting oxygen index compared with the original polymer. A new class of polymerizable ultraviolet stabilizers has also been developed; these stabilizers are styryl, α-methylstyryl, acryloyl and methacryloyl derivatives of 2(2-hydroxyphenyl)2H-benzotriazoles. These monomers have been copolymerized with styrene, acrylates and methacrylates. 2(2-Hydroxyphenyl)2H-benzotriazoles substituted in the 4 position of the benzotriazole ring with hydroxyl, acetoxy or carboxyl groups suitable for incorporation into polyesters, polycarbonates, polyamides and epoxy resins have also been synthesized. All 2(2-hydroxyphenyl)2H-benzotriazole ultraviolet absorbers and the polymers into which they are incorporated have high light absorbency with γ_max between 330 and 350 nm and extinction coefficients in some cases as high as 4.5 × 10⁴ 1 mol^?1 cm^?1.     

Experimental investigation of related properties of asphalt binders containing various flame retardants

The improved flame retardancy of asphalt binders containing various kinds of flame retardants including antimony trioxide, decabromodiphenyl ether (EBPED), aluminium trihydroxide (ATH) and zinc borate (ZB) under different additive concentrations was investigated by limited oxygen index (LOI) and differential scanning calorimetry (DSC) test. To assess the effects of the type and concentration of the flame retardants on rheological properties of asphalt binders, the softening point, penetration, ductility, storage stability and viscosity were tested. The thin film oven test (TFOT) was used to investigate the effect of short-term oxidation on flame-resistant asphalt binders. Experimental results indicated that all of selected flame retardants had a relatively small effect of rheological properties of the asphalt binders, but a great effect on flame retardancy. Asphalt binder with LOI of 25.9 was obtained by adding 6 wt% mixed flame retardants of EBPED: antimony trioxide: ZB=3:1:1 by mass. Asphalt binder was transformed from inflammable materials into flame retardant materials. Therefore, the asphalt binder with both good flame retardancy and rheological properties is a novel road functional material to meet two respects' demands as flame retardant materials and road materials at the same time.     

无卤阻燃剂的研究进展

通过对磷系、氮系、硅系和膨胀型石墨阻燃剂阻燃机理的分析,论述了无卤阻燃剂的发展动向及几种具有发展前途的新型阻燃剂,阐明了无卤、高效、低烟、低毒、环保型阻燃剂的研究是阻燃剂的发展方向.     

PET纤维及其织物的阻燃技术进展

概述了聚对苯二甲酸乙二醇酯(PET)纤维及其织物的阻燃技术,包括共缩聚阻燃PET纺丝、PET与阻燃剂共混纺丝及PET织物阻燃后处理等。其中,阻燃剂主要有磷系及磷-氮系阻燃剂,如:9,10-二氢-9-氧杂-10-磷杂蒽-10-氧化物(DOPO)衍生物、次膦酸(酯)及其聚合物、氧化膦聚合物、膦酸酯及螺环磷酸酯等。今后应积极开发生态和环境兼容的阻燃PET纤维新技术。     

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     

我国无机阻燃剂研究及应用进展

介绍了我国氢氧化铝、氢氧化镁、无机磷化合物、硼酸盐、氧化锑、钼化合物等主要无机阻燃剂品种的应用和研究进展，并根据现状提出了有针对性的发展方向与建议。     

氯氧化锑阻燃剂的制备、阻燃机理及其阻燃应用

对氯氧化锑的不同制造方法作了详细比较 ,指出开发新的生产工艺是把氯氧化锑阻燃剂推向市场的关键 ;在分析氯氧化锑阻燃机理的基础上 ,探讨了其阻燃应用。     

Flame resistance and foaming properties of NBR compounds with halogen‐free flame retardants

Acrylonitrile butadiene rubber (NBR) foams compounded with various halogen‐free flame retardants were prepared. The influence of nonhalogen flame retardants on the flame resistance and foaming properties of the NBR compounds were investigated. The foaming properties (expandability 980%–1050%, closed‐cell structure) of NBR compounds with expandable graphite (EG) and ammonium polyphosphate (APP) flame retardants were similar to the NBR base compounds which contained primarily aluminum hydroxide (ATH). The heat release capacity (HRC) ranged from 10 to 74 J/g‐K, the average heat release rate (A‐HRR) ranged from 8 to 60 kW/m², and the total heat release (THR) ranged from 2.6 to 7.3 MJ/m² for the nonhalogenated NBR foams with closed‐cell structure and were significantly decreased upon increasing the amounts of flame retardants. This reduction is attributed to the hard char formation and production of water from the interaction with ATH. The limiting oxygen index (LOI) and time to ignition (TTI) show opposite results. The smoke density (0.050–0.037) of the NBR foams with EG flame retardant was decreased when compared to the NBR foam (0.107). The EG flame retardant was more effective than the phosphorus/nitrogen flame retardants in reducing the HRR and smoke density. The use of both ATH and EG is very effective in improving flame resistance. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers     

氯氧化锑阻燃剂研究进展

与Sb2 O3 及NaSb(OH) 6 等锑系阻燃剂比较 ,氯氧化锑阻燃剂具有能大幅度地降低色料用量和显著提高透明度的特点 ,若要将其推向市场 ,关键在于开发新的生产工艺 ,降低生产成本。本文比较了氯氧化锑阻燃剂的各种制造方法 ,综述了氯氧化锑阻燃剂的阻燃机理及其阻燃应用     

Ecological Aspects of Polymer Flame Retardation

Abstract

The practical application of commercial polymer flame retardant can no longer meet alone the present requirements either in terms of effectiveness or hazard. The most effective flame retardants so far are halogen, phosphorous, antimony and heavy metal based compounds which however have the most environmental impact either while they perform their action or when burned in incineration of waste containing fire retardant polymeric materials.

The practical search of new ecologically-friendly flame retardants requires cooperation between industrial and academic research. This presentation is devoted to only some of new trends in this very important task: Polymer Char Formers, Low-rflelting Glasses Systems, Morphological Modifications.     

建筑用阻燃聚氨酯研究进展

综述了有机阻燃剂对硬质聚氨酯泡沫塑料的阻燃改性研究进展。其中有机阻燃剂主要有磷系、氮系、磷/氮复合型等,其中磷/氮复合型的阻燃剂的改性效果要明显高于单一磷系或单一氮系的改性效果。另外,将有机阻燃剂与无机阻燃剂进行复配,利用有机和无机之间的协同作用,能够有效地提高聚氨酯的极限氧指数,降低其发烟量和热释放速率,而且还会在一定程度上影响到聚氨酯泡沫塑料的密度、热导率和压缩强度等性能。并指出复配性阻燃剂将是今后的研究方向。     

成炭剂和分子筛协同MPP对PA6的阻燃性研究

将聚磷酸三聚氰胺(MPP)作为阻燃剂阻燃PA6,研究了高效成炭(剂CFA)和4A分子筛对MPP阻燃PA6性能的影响,并通过热失重分(析TGA)对材料进行了表征。结果表明:CFA和4A分子筛对MPP具有协效阻燃作用,加速了PA6阻燃时的成炭化学反应,改善了炭层结构。当阻燃体系中添加26%的MPP、4%的CFA和2%的4A分子筛时P,A6的氧指数可达到35%,垂直燃烧通过UL94 V—1级。     

Highly flame-retarding cotton fabrics with a novel phosphorus/nitrogen intumescent flame retardant

A novel phosphorus/nitrogen intumescent flame retardant, namely 6-chloro-4-(diethylamino phosphorate phosphoryl chloride)-2-(sodium 4-aminobenzensulfonate)-1,3,5-triazine (APPCABT), has been synthesized and characterized by elemental analysis, FT-IR, ¹H-NMR and ³¹P{H}-NMR spectroscopies. To investigate the flame-retarding properties of the treated cotton fabrics, APPCABT was applied to the chemical treatment of the cotton fabrics surface. The flame-retarding performance of the treated samples with APPCABT was evaluated by limiting oxygen index (LOI). The thermal degradation behavior of the treated samples was studied using thermogravimetric analysis (TGA). The surface morphology of the treated samples was observed by scanning electron microscopy (SEM). These results show that APPCABT is both an intumescent flame retardant with high efficiency and an excellent char-forming agent for the flame-retarding treatment of cotton fabrics.     

Thermal stabilities and flame retardancies of phloroglucinol‐based organo phosphates when applied to polycarbonate

A series of organo phosphorus flame retardants (FRs) based on aromatic phosphate and cyclic phosphate were synthesized in an attempt to develop an efficient FR for polycarbonate. Their successful synthesis was confirmed by FT‐IR and ¹ H and ³¹P NMR. Their thermal stability and flame retarding efficiency as a single‐component additive were investigated and compared with the commercial FR, resorcinol bis(diphenyl phosphate). The thermogravimetric analysis results revealed that the aromatic phosphate synthesized in this study, phloroglucinol diphenyl phosphate (PDP), shows a higher thermal degradation temperature and better flame retardancy even though it has a lower P content than cyclic phosphate‐based FRs. The flame retarding efficiency was evaluated by the UL‐94 test method. The V‐0 rating was achieved at a PDP loading of 2 wt% in polycarbonate in the presence of an anti‐dripping agent (1 wt%), which is better than that of resorcinol bis(diphenyl phosphate) and cyclic phosphate‐based FRs. The high thermal stability and P–OH generation tendency is responsible for the better flame‐retarding performance of PDP. The degradation path of PDP is also discussed. Copyright © 2012 John Wiley & Sons, Ltd.     

Synergistic effect of carbon and phosphorus flame retardants in rigid polyurethane foams

Two kinds of carbon and phosphorus synergistic system used to improve the flame retardancy of rigid polyurethane foams (RPUF) were studied. One is the synergistic effect of expandable graphite and guanidinium phosphate; the other is red phosphorus and guanidinium phosphate. The flame retardant properties and mechanical properties of these composites were investigated by limiting oxygen index, cone calorimeter test, as well as tension and compression test. These 2 groups of mixed inorganic flame retardants can greatly improve the flame retardancy of RPUF composites, as the limiting oxygen index increases from 20.1% to about 33% and the HRR reduces from 395 kW/m² to below 200 kW/m². It provides a convenient and inexpensive way to obtain RPUF with demanding properties.     

尼龙6/弹性体合金的阻燃改性研究

分别采用环保阻燃剂十溴二苯乙烷(DBPE)/三氧化二锑(Sb2O3)和聚磷酸铵(APP)对PA6/POE-g-MAH合金进行阻燃改性,同时以纳米有机蒙脱土(OMMT)作为辅助阻燃剂,讨论了阻燃剂种类、用量和配比对合金燃烧性能和力学性能的影响.结果表明:DBPE/Sb2O3在该体系中具有比APP更高的阻燃效率;OMMT与DBPE/Sb2O3和APP在合金的阻燃改性方面具有一定的协同效应;所有阻燃成分对合金的韧性均产生负面影响;DBPE/Sb2O3和APP使得体系的拉伸强度下降,而OMMT发挥了一定的补强作用;当DBPE/Sb2O3与APP组成的复配阻燃体系中二者的用量分别为10份和40份时,合金具有较好的综合性能.     

Influence of the molecular weight of PPO resins and char-forming behavior of polymeric additives on the flame retardancy of EPDM formulations

The influence of the molecular weight of poly(2,6-dimethylphenylene oxide) (PPO) on the flame retardancy of ethylene–propylene–diene-modified elastomer (EPDM) formulations containing melamine, kaolin, and PPO formulations was studied. The influence of the molecular structures of various char-forming polymers on their flame-retardant effect was also investigated. PPO resins having number-average molecular weight (M_n) from 3200 to 24,800 and weight-average molecular weight (M_w) 9000 to 58,400 affected the oxygen index (OI) values and UL 94 ratings of EPDM formulations, and the preferable molecular weight was found to be about M_n 13,300 and M_w 29,200. Among the char-forming polymeric additives studied, PPO was most effective in providing flame retardancy. The concept of char-forming rate is proposed to explain the variation in the observed flame retardancy. Higher char-forming rate (in contrast to char yield) correlated well with higher OI and better UL 94 ratings in these systems. The melting-before-charring character of char-forming polymers was another important factor that appeared to control char morphology and thus flame retardancy. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1405–1414, 1998