新型增韧阻燃酚醛树脂泡沫塑料的研制

以聚磷酸铵(APP)、三聚氰胺(MEL)和季戊四醇(PER)为阻燃剂,聚乙二醇和玻璃纤维改性酚醛树脂为基体,制备改性阻燃酚醛泡沫塑料。通过对改性基体材料进行红外分析,对改性阻燃泡沫塑料进行扫描电镜、冲击强度、热稳定性以及阻燃性能测试,确定了聚乙二醇与复合阻燃剂用量对泡沫塑料性能的影响。结果表明:酚醛树脂100份,聚乙二醇12份,复合阻燃剂15份,制备的改性阻燃酚醛泡沫塑料具有优异的韧性和阻燃性能,其冲击强度为5.54 kJ/m2,达到B1难燃材料的标准。     

阻燃改性酚醛树脂泡沫的制备及性能

在酚醛树脂泡沫传统制备工艺基础上,分别加入2-羧乙基苯基次磷酸、磷酸三甲苯酯、羟基乙叉二膦酸(HEDP)、硅酸钠、三聚氰胺五种阻燃剂,制备改性酚醛树脂泡沫。研究了阻燃剂对酚醛树脂泡沫发泡率和极限氧指数的影响,并用热重分析仪和红外光谱仪进行表征。结果表明:HEDP对酚醛树脂泡沫发泡率影响最小,极限氧指数提高最高,因此,HEDP适合作为酚醛树脂泡沫的阻燃剂;添加20%(w)HEDP的改性酚醛树脂泡沫极限氧指数为63.5%,具有更好的阻燃效果。     

摩擦材料用改性酚醛树脂的制备及应用

用三聚氰胺、腰果酚、粉末丁腈橡胶对酚醛树脂进行了改性,并将其用作摩擦材料的基体树脂。探讨了腰果酚、三聚氰胺用量等因素对改性酚醛树脂性能的影响,并对各摩擦制动材料的摩擦磨损、热衰退等性能进行了研究。结果表明:腰果酚、丁腈橡胶改性酚醛树脂(YX-PF)与三聚氰胺、腰果酚改性酚醛树脂(SY-PF)的热分解温度比普通酚醛树脂分别提高了57℃和91℃,且摩擦磨损性能优良。另外,加入丁腈橡胶可进一步提高SY-PF的综合性能。     

含氟磷酸盐型离子液体对软质聚氨酯的协效阻燃研究

制备了复合阻燃软质聚氨酯泡沫(FPUF),研究了三聚氰胺聚磷酸盐(MPP)、可膨胀型石墨(EG)和离子液体(IL)对FPUF泡沫的阻燃影响。利用氧指数(LOI)确定3种复合阻燃剂的最佳配比,通过热重(TG)和锥形量热(CCT)分析了阻燃剂对FPUF的阻燃和热稳定性的影响。结果表明,当MPP、EG、IL的质量比为7.5∶7.5∶2时,制备的阻燃FPUF的LOI达到最高27.5%;TG显示了FPUF/MPP/EG/IL的残炭量高于纯FPUF和FPUF/MPP/EG;CCT表明了热释放速率峰值和总热逐渐降低,烟释放量及CO生成率减少;因离子液的添加使炭层更加致密,3种阻燃剂协效阻燃,改善了阻燃效果,降低了火灾危险性。     

无卤阻燃尼龙66的研究

采用分子复合改性三聚氰胺氰尿酸盐(M-MCA)为阻燃剂制备了无卤阻燃(非增强)尼龙66(PA66).研究表明:与传统三聚氰胺氰尿酸盐(MCA)相比,M-MCA阻燃PA66具有自熄时间短、熔滴无火焰的特点,在8％添加量时即可通过UL94V-0( 1.6 mm)阻燃级别,阻燃材料力学性能优良,综合性能良好.采用热重分析仪(TGA)、微型量热仪(MCC)对材料燃烧成炭行为进行分析,研究其阻燃机理.     

三聚氰胺聚磷酸盐/硼酚醛协效体系阻燃PA66/GF复合材料的研究

采用氮磷型阻燃剂三聚氰胺聚磷酸盐(MPP)与硼改性酚醛树脂(BPF)组成的复合阻燃体系对玻纤(GF)增强尼龙66( PA66)复合材料进行阻燃,获得了阻燃性能优异、力学性能良好的增强复合材料,研究了协效阻燃剂BPF/MPP配比、BPF/MPP用量及GF用量对阻燃复合材料阻燃性能的影响,采用微型燃烧量热和质量保持率分析方法研究了阻燃复合材料的燃烧及成炭行为,对复合阻燃剂的协效机理进行了讨论.结果表明,当BPF在BPF/MPP中的质量分数为15％时,添加25％ BPF/MPP复合阻燃剂可使20％ GF增强PA66复合材料达到V-0( 1.6 mm)阻燃级别,极限氧指数增加至25.3％,拉伸强度、弯曲强度、缺口冲击强度分别为116 MPa,132 MPa,7.1 kJ/m2.该复合材料可满足高性能无卤阻燃的使用要求.     

十溴二苯乙烷协同三氧化二锑阻燃PE研究

通过采用新型阻燃剂十溴二苯乙烷(DBDPE)与Sb2O3复合对PE进行阻燃改性，研究了DBDPE与Sb2O3的协同效应，复合阻燃剂对PE阻燃性能、热解性能、物理机械性能的影响。结果表明，DBDPE／Sb2O3复合阻燃剂对PE有良好的阻燃作用。     

硅烷偶联剂改性酚醛树脂的合成

以硅烷偶联剂KH560作为改性剂,采用化学合成方法合成了KH560改性酚醛树脂。通过傅里叶变换红外光谱、热重分析以及力学性能测试研究了硅烷偶联剂KH560对酚醛树脂热性能和力学性能的影响。结果表明:当w(KH560)为2.5%时,改性酚醛树脂在318℃时开始分解,树脂质量损失约为17.0%,耐热性能较好;与改性前相比,改性酚醛树脂的拉伸强度提高了32.9 MPa,冲击强度提高了4.03 kJ/m~2,力学性能得到了改善。     

十溴二苯乙烷阻燃改性聚丙烯的研究

采用新型阻燃剂十溴二苯乙烷(DBDPE)与三氧化二锑(Sb2O3)复合对PP进行阻燃改性,研究了DB DPE与Sb2O3的协同效应,复合阻燃剂对PP阻燃性能、物理机械性能的影响及其阻燃机理。结果表明DBDPE Sb2O3复合阻燃剂对PP有良好的阻燃作用。     

MUF共缩合树脂的研制

为缓解苯酚紧缺,进行了用三聚氰胺改性脲醛树脂(MUF树脂)取代酚醛树脂生产室外级胶合板的研究。考查了三聚氰胺用量、反应工艺条件及增粘剂对MUF树脂性能的影响。抽样做胶合板耐候性试验表明,MUF树脂可取代酚醛树脂。     

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     

阻燃剂对热固性酚醛树脂阻燃性能影响的研究

通过氧指数、垂直燃烧等级及产烟率测定研究了氢氧化铝(ATH)、氢氧化镁(MH)、膨胀石墨(EG)、膨胀型阻燃剂(IFR)等以单一或协同复配的形式对酚醛树脂(PF)体系阻燃性能的影响,并采用差热分析(DTA)对体系的微观热行为进行了研究。结果表明,放热量最小的体系为ATH/MH/EG/PF,ATH/MH/EG/IFR/PF体系的氧指数最大,达到96。ATH/MH/PF体系的产烟率最低(72%)。添加阻燃剂后,体系的垂直燃烧等级可提高到UL94V-0级。     

苯并嗯嗪树脂阻燃改性研究进展

苯并嗯嗪是一类经开环聚合得到的新型酚醛树脂,具有良好的耐热性、阻燃性,并且在固化时不释放出小分子物质。苯并嗯嗪虽然具有较好的阻燃性能,但仍不能满足某些应用场合需要。本文介绍了舍磷、含硅以及含其他官能团的阻燃剂用于苯并嗯嗪体系的阻燃效果。     

High-efficiency ammonium polyphosphate intumescent encapsulated polypropylene flame retardant

The flame retardant polypropylene containing the micro-envelope core-shell structure flame retardant, which encapsulated ammonium polyphosphate into melamine-formaldehyde resin and sodium silicate through in situ polymerization was prepared with polyamide 6, added as a carbon-forming agent. The composition of ammonium polyphosphate, encapsulated ammonium polyphosphate with melamine-formaldehyde resin and the micro-envelope core-shell structure flame retardant were characterized. The fire safety and thermal stability were investigated and showed an improvement including limiting oxygen index, thermogravimetric analysis, vertical burning tests, and microscale combustion calorimeter. The burned compounds were also studied to confirm the burning mechanism. The results showed the flame retardant performance had been greatly improved, while polyamide 6 had better char-forming effect. Besides, the water solubility of flame retardants and their influence on the mechanical properties of polypropylene were also investigated. The results on the effects of additives demonstrated a high efficiency flame retardant to polypropylene. A core-shell flame retardant that sodium silicate and melamine-formaldehyde resin-coated ammonium polyphosphate had been constructed. The effect of the built flame retardant system on the combustion performance of polypropylene was studied from the mechanism and performance. The LOI of the most flame retardant polypropylene reached 28.6%, and UL-94 reached the V-0 level.     

酚醛在丙烯酸树脂防火改性中的应用

以酚醛树脂为主防火剂、胺类为协效剂,研究了其种类、用量对丙烯酸树脂防火性能的影响,采用锥形量热仪和热重分析仪对酚醛改性丙烯酸树脂的燃烧性能和热稳定性进行了测试,并对燃烧后的炭层结构进行了电镜分析。结果表明,硼酚醛树脂能显著提高丙烯酸树脂的防火性能,硅酸铝、六次甲基四胺具有有良好的协效作用;当丙烯酸树脂与硼酚醛树脂质量比为50:50,硅酸铝质量分数为7%,六次甲基四胺为2%时,改性树脂耐燃时间达到39min,点燃时间(TTI)及热释放速率峰值出现时间明显延长,热释放速率明显降低,800℃时残炭率为45%,热稳定性明显提高,燃烧烧后形成了表面为致密网状、断面为微细泡孔状的炭层结构,防火性能提高。     

Thermal studies on paper treated with flame‐retardant

Sodium silicate and sodium borate were tested as flame retardants on two types of paper sheet (100% rice straw pulp paper with a high silica content while the other consisted of 100% wood pulp paper). After addition of inorganic flame retardant salts (sodium silicate and sodium borate) on to the two samples of paper, the thermal behaviour of the treated paper sheets revealed differences in the course of the differential thermal analysis curves. The thermal analysis studies were carried out under an oxidizing atmosphere using differential thermal (DTA) and thermogravimetric (TGA) analysis. The flame retardants used in this study reduced the amount of volatile products formed during decomposition of the paper and increased the weight loss due to formation of char for the treated papers. The thermal degradation of paper can be considered as a first order degradation. Two stages of thermal degradation were kinetically differentiated, namely, a volatilization stage and a decarbonization stage. The activation energy for these two stages were calculated. The addition of flame‐retarding salts decreased the activation energy for both stages. Sodium silicate salt showed more reduction of activation energy than sodium borate, especially for the rice straw paper. Copyright © 1999 John Wiley & Sons, Ltd.     

Melamine poly(metal phosphates) as flame retardant in epoxy resin: Performance,modes of action,and synergy

Melamine poly(metal phosphates) (MPMeP) are halogen‐free flame retardants commercialized under the brand name Safire. Melamine poly(aluminum phosphate) (MPAlP), melamine poly(zinc phosphate) (MPZnP), and melamine poly(magnesium phosphate) (MPMgP) were compared in an epoxy resin (EP). The thermal decomposition, flammability, burning behavior, and glass transition temperature were investigated using thermogravimetric analysis, pyrolysis combustion flow calorimeter, UL 94 testing, cone calorimeter, and differential scanning calorimetry. While the materials exhibited similarities in their pyrolysis, EP + MPZnP and EP + MPMgP showed better fire behavior than EP + MPAlP due to superior protective properties of the fire residues. Maintaining the 20 wt % loading, MPZnP was combined with various other flame retardants. A synergistic effect was evident for melamine polyphosphate (MPP), boehmite, and a derivative of 6H‐Dibenzo[c,e][1,2]oxaphosphinine‐6‐oxide. The best overall performance was observed for EP + (MPZnP + MPP) because of the best protection effectiveness of the fire residue. EP + (MPZnP + MPP) achieved V1/V0 in UL 94, and an 80% reduction in the peak heat release rate. This study evaluates the efficiency of MPMeP in EP, alone and in combination with other flame retardants. MPMeP is a suitable flame retardant for epoxy resin, depending on its kind and synergists. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43549.     

PBT/TPU/DOPO-MA阻燃复合材料的制备及性能

通过使用9,10-二氢-9-氧杂-10-磷朵菲-10-氧化物（DOPO）和马来酸酐反应合成制备DOPO衍生物阻燃剂DOPO-MA,并且其结构使用傅里叶红外光谱分析（FTIR）和核磁共振氢谱分析（¹H NMR）技术进行表征。将阻燃剂与聚对苯二甲酸丁二醇酯（PBT）和热塑性聚氨酯（TPU）熔融共混以制备PBT/TPU/DOPO-MA阻燃复合材料。通过运用锥形量热、UL-94、极限氧指数（LOI）、热重分析（TGA）、差热分析（DSC）和力学测试,研究了阻燃剂对复合材料的性能影响。测试结果表明,PBT/TPU/DOPO-MA复合材料具有良好的阻燃性能,加入10％DOPO-MA后,LOI从23.2增加到31.6,可达到UL-94 V-1等级,热释放率峰值（PHRR）和最大成热辐射速率（MAHRE）值降低;热重分析测试结果表明,添加DOPO-MA可以使得阻燃复合材料的热稳定性有显著的提高,当加入10％DOPO-MA后,残炭量可从6.87增加到14.36。此外,随着DOPO-MA含量的增加,阻燃复合材料的结晶度可得到一定的提高。     

Investigation on flame retardancy and rheological and thermomechanical characterisation of multiwall carbon nanotube reinforced nanocomposites

Abstract

In the present work, the influence of multiwalled carbon nanotubes (MWCNTs) on the flame retardancy and rheological, thermal and mechanical properties of polybutilen terephthalate (PBT) and polypropylene (PP) matrixes has been investigated. The carbon nanotube content in the thermoplastic materials was 2 and 5?wt‐%. The nanocomposites were obtained by diluting a masterbatch containing 20?wt‐% nanotubes using a twin‐screw extruder and the thermal properties were analysed by differential scanning calorimetry and thermogravimetric analysis; thermomechanical properties were determined by dynamic mechanical thermal analysis and the rheological behaviour was studied by a Thermo Haake Microcompounder. The results concerning the flame retardancy show that the MWCNTs are not equally effective as flame retardants in PP and PBT. The ignition time is increased only for PBT whereas the extinguishing time is decreased for PP and PBT. The reinforcement of the thermoplastics with multiwall carbon nanotubes is improved regarding the mechanical and thermal properties of the nanocomposites compared to pristine materials and the behaviour of thermoplastic nanocomposites regarding fire retardancy depends on the nature of the polymeric matrix.     

含磷阻燃剂阻燃环氧树脂热降解动力学

以2-二苯基膦酰基-1,4-苯二酚(DPO-HQ)为阻燃剂制备了阻燃环氧树脂,利用动态热重分析法(TGA)研究了纯环氧树脂(EP)和阻燃环氧树脂(FR-EP)在不同升温速率下的热稳定性,建立了EP和FR-EP体系的动力学模型和非模型动力学(MFK),并对比分析了模型动力学和非模型动力学对于描述EP体系和FR-EP体系的适用性.结果表明:阻燃剂的引入降低了环氧树脂初始降解温度,但增加了残炭率.由Flynn-Wall-Ozawa方法和Coats-Redfern方法建立的模型动力学表征EP和FR-EP体系高温降解过程中误差较大,而非模型动力学能更准确地预测和描述EP和FR-EP体系的高温降解行为.