DOPO基低聚物与介孔二氧化硅协同阻燃环氧树脂

采用介孔二氧化硅(MS)与9,10–二氢–9–氧杂–10–磷杂菲–10–氧化物基低聚物(PDAP)对环氧树脂(EP)进行阻燃,制备阻燃环氧固化物。通过热重分析、极限氧指数(LOI)和UL–94测试对固化物的热稳定性和阻燃性能进行研究,并利用红外光谱、裂解–气相色谱/质谱联用仪和扫描电子显微镜对MS与PDAP的协同阻燃机理进行研究。结果表明,PDAP与MS存在较好的协同阻燃作用,当4%的PDAP和0.5%的MS添加至EP中,得到的固化物在燃烧时出现剧烈的吹熄现象,其LOI值高达34.3%,并通过UL–94的V–0级测试。在凝聚相,PDAP降解产生的磷酸类物质与MS反应生成磷硅酸盐,促进生成富磷、硅的致密炭层。在气相的阻燃机理主要是含磷自由基的猝灭作用和难燃气体的稀释作用。     

两种不同橡胶粒径的ABS树脂协同作用研究

采用两种不同橡胶粒径的丙烯腈-丁二烯-苯乙烯共聚物(ABS)掺混制备橡胶粒子尺寸双峰分布的ABS树脂。恒定ABS树脂的橡胶含量,通过调节不同粒径橡胶的质量比,考察其对ABS树脂力学性能的影响,并利用扫描电子显微镜和透射电子显微镜观察了ABS树脂的微观结构,分析了协同作用的增韧机理。结果表明,ABS树脂的冲击强度和屈服强度都随着大粒径橡胶粒子比例的减少而增大;当L-PB/S-PB为1/9时,ABS树脂的冲击强度和屈服强度最高,两种橡胶粒子发生了明显的协同作用。     

Design of Hierarchically Tailored Hybrids Based on Nickle Nanocrystal-Decorated Manganese Dioxides for Enhanced Fire Safety of Epoxy Resin

A novel and hierarchical hybrid composite (MnO₂@CHS@SA@Ni) was synthesized utilizing manganese dioxide (MnO₂) nanosheets as the core structure, self-assembly chitosan (CHS), sodium alginate (SA) and nickel species (Ni) as surface layers, and it was further incorporated into an epoxy matrix for achieving fire hazard suppression via surface self-assembly technology. Herein, the resultant hybrid epoxy composite possessed an exceptional nano-barrier and synergistic charring effect to aid the formation of a compact layered structure that enhanced its fire-resistive effectiveness. As a result, the addition of only 2 wt% MnO₂@CHS@SA@Ni hybrids led to a dramatic reduction in the peak heat release rate and total heat release values (by ca. 33% and 27.8%) of the epoxy matrix. Notably, the peak smoke production rate and total smoke production values of EP/MnO₂@CHS@SA@Ni 2% were decreased by ca. 16.9 and 38.4% compared to the corresponding data of pristine EP. This was accompanied by the suppression of toxic CO, NO release and the diffusion of thermal pyrolysis gases during combustion through TG-IR results. Overall, a significant fire-testing outcome of the proposed hierarchical structure was proven to be effective for epoxy composites in terms of flammability, smoke and toxicity reductions, optimizing their prospects in other polymeric materials in the respective fields.     

Effect of Bio-Based Cobalt Alginate on the Fire Safety and Mechanical Properties for Epoxy Resin

There is a growing demand to develop epoxy resins (EP) with smoke suppression as well as satisfactory flame retardancy. Herein, bio-based cobalt alginate is successfully fabricated and incorporated into EP to prepare EP/Cobalt Alginate composites with better fire safety performance. The addition of cobalt alginate reduces the thermal-decomposition rate, temperature at maximum weight-loss rate of EP, whereas obviously improves the thermal stabilities at a higher temperature range. Furthermore, the addition of cobalt alginate substantially reduces the fire hazard of EP, resulting in 56.2% reduction in peak heat release rate, as well as 17.8% and 56.3% reduction in total smoke production and peak smoke production rate, respectively, compared with EP matrix. Moreover, the presence of cobalt alginate increases smoke-suppressant properties, according to the smoke density test. Additionally, the incorporation of cobalt alginate has no obviously destructive effect on the mechanical properties of EP, while EP/Cobalt Alginate-3 exhibits a 27.0% improvement in impact strength. In prospective, this study may provide a significant method for producing eco-friendly flame retardant EP.     

SnO2和SiO2用于PVC的阻燃消烟及协同作用

研究了二氧化锡和二氧化硅对软PVC阻燃消烟性的影响。通过对极限氧指数、剩炭率、烟密度的测定和DTATG曲线的分析证明,添加8g二氧化锡/二氧化硅复合阻燃剂的PVC的氧指数和剩炭率比未添加的分别增高5.5个单位和4.1%,烟密度降低16.4%,降解活化能分别降低38kJ/mol和23.1kJ/mol,从而证明二氧化锡/二氧化硅复合阻燃剂对于PVC是一种很好的阻燃消烟剂,二氧化锡和二氧化硅有很好的协同作用。同时证明这种复合阻燃剂能代替三氧化二锑,使产品的成本进一步降低。     

A DOPO Derivative Constructed by Sulfaguanidine and Thiophene toward Enhancing Fire Safety,Smoke Suppression,and Mechanical Properties of Epoxy Resin

In order to eliminate the negative effect of traditional 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) -based flame retardants on heat resistance, mechanical properties, and curing process of epoxy resin (EP), a DOPO derivative (DST) constructed by sulfaguanidine and thiophene is designed and used as co-cured agent for EP. Compared with EP, the maximum decrease of glass transition temperature (T_g) in all EP/DST samples is less than 5%, indicating EP modified by DST maintains good heat resistance. Encouragingly, DST shows satisfactory flame-retardant efficiency and excellent smoke suppressing effects. EP containing barely 5 wt% of DST (P content: 0.37 wt%) achieves a UL-94 V-0 rating and 32.8% limited oxygen index (LOI) value. Its peak heat release rate (PHRR), total heat release (THR), and total smoke production (TSP) are also decreased by 31.2%, 18.8%, and 30.2% . Further, DST significantly improves mechanical properties of the EP/DDM/DST system. The tensile strength and modulus increase by 37.2% and 14.6%, respectively, as DST content is 7.5 wt%. It is revealed that DST has positive quenching and diluting effects in the gas phase, as well as promoting the formation of a compact char layer in the condensed phase.     

掺镧介孔纳米球降低烟气中低分子醛酮类物质的研究

改进传统的合成六方介孔材料的工艺,合成具有双纳米效应的掺镧介孔纳米球,以此作为卷烟添加剂,研究了其对红塔山经典1956卷烟主流烟气中含有的低分子醛酮化合物的吸附行为.结果表明在过滤嘴中加入了添加剂的烟样中8种低分子醛酮的含量明显低于没有加入添加剂的烟样,且测定结果的相对偏差小于0.3％.其中,甲醛的含量由186.0721μg/支减少到103.698μg/支,说明该掺镧介孔纳米球添加剂对甲醛的吸附具有较好的选择性.     

分子间磷杂菲与磷腈双基协同阻燃环氧树脂研究

将六苯氧基环三磷腈(HPCP)和9,10–二氢–9–氧杂–10–磷杂菲–10–氧化物(DOPO)复合应用于阻燃环氧树脂(EP),通过极限氧指数和垂直燃烧性能测试、热失重分析、锥形量热分析等研究了其协同阻燃EP的性能,探讨了协同阻燃机理。结果表明,当DOPO在HPCP/DOPO复合阻燃剂中所占比例达到80%时,样品的阻燃级别达到UL94 V–0级,总热释放量降低,优于两种阻燃剂单独使用条件下对EP的阻燃效果,表明磷腈和磷杂菲两种阻燃剂之间存在着协同阻燃效应。     

The Effect of Different Smoke Suppressants with APP for Enhancing the Flame Retardancy and Smoke Suppression on Vinyl Ester Resin

Flame retarded and smoke suppressed vinyl ester resin (VER) were prepared through ammonium polyphosphate (APP) coupled with different smoke suppressants. The flame retardancy of these composites was tested by the limiting oxygen index and UL-94 tests. The typical combustion parameters including heat release rate (HRR), peak of HRR (p-HRR), total heat release, smoke production rate, and total smoke production were detected using a cone calorimeter. The smoke suppressants CaCO₃, ZnMoO₄, Cu₂O, and Fe₂O₃ show different effect on flame retardancy and smoke suppression of VER composites when they are coupled with APP, the synergistic action of APP and CaCO₃ is more effective on decreasing the HRR and smoke release rate than several other smoke suppressants. This is attributed to the fact that CaCO₃ could promote the formation of a dense carbon layer with high thermal stability and anti-oxidation property, which could act as an effective physical barrier. The flame retardant performances and mechanisms of APP and CaCO₃ were evaluated and analyzed at length by thermogravimetric coupled with a Fourier transform infrared spectrometer (FTIR), scanning electron microscopy, FTIR, and X-ray diffraction. POLYM. ENG. SCI., 60: 314–322, 2019. © 2019 Society of Plastics Engineers     

三聚氰胺对硬质聚氨酯泡沫塑料的阻燃与消烟作用

硬质聚氨酯泡沫塑料广泛用于高层建筑的外保温,但由于它易燃且放出有毒气体而对人体和环境造成危害。研究了三聚氰胺对硬质聚氨酯泡沫塑料的阻燃及消烟作用。     

Synergistic Effects of Iron Alginate on Improving the Fire Safety and Mechanical Properties of Epoxy Resin/Ammonium Polyphosphate Composites

Iron alginate is chosen as an eco-friendly synergist to improve the flame retardancy, smoke suppression, and mechanical properties of epoxy resin/ammonium polyphosphate composites (EP/APP). The suitable additive amount of iron alginate further enhances the char-forming ability in the higher-temperature range and flame retardancy of EP/APP. EP/APP_9.0-iron alginate_1.0 retains a char residue of 33.3% at 700 °C and obtains a limiting oxygen index value of 28.4% and vertical burning test (UL-94) V-0 rating, while EP/APP₁₀ has no UL-94 rating. The burning behaviors of EP/APP_9.0-iron alginate_1.0 are also suppressed; and the total smoke production value is much lower than that of EP/APP₁₀. EP/APP_9.0-iron alginate_1.0 releases less smoke and flammable fragments. The suitable additive amount of iron alginate boosts the mechanical properties of EP/APP, while APP destroys the mechanical properties of EP. Therefore, the addition of suitable amount of iron alginates can further reduce the fire hazard, and improve the mechanical properties of EP/APP composites.     

氧化石墨烯在膨胀型水性防火涂料中阻燃和抑烟作用研究

以水性丙烯酸乳液为成膜物质,钛白粉为颜料,加入不同量氧化石墨烯(GO)纳米粒子作为协效阻燃/抑烟剂配制膨胀型防火涂料,采用大板燃烧法、锥形量热仪和烟密度测试法对其阻燃和抑烟效果进行了研究。结果表明:GO能有效地提高涂料试样的耐燃时间和降低峰值生烟速率(p SPR),当GO添加量为0.025份时(以100份乳液计,下同),试样耐燃时间可以增加59.5%,当添加量为0.125份时试样的p SPR从0.024 m2/s降至0.013 m2/s。结合扫描电镜(SEM)、热重分析(TG)、差热分析(DTA)和红外光谱(FT-IR)等手段对试样炭层的结构形貌进行分析后发现,具有片状结构的氧化石墨烯在涂料受热膨胀过程中会使自身和基体分子链取向,进而在聚合物炭化过程中形成骨架结构增加炭层强度,达到阻燃和抑烟的目的。     

海泡石与APP对PVC/竹粉复合材料的阻燃抑烟机理

将海泡石(SEP)和聚磷酸铵(APP)同时加到聚氯乙烯(PVC)/竹粉复合材料中,考察SEP和APP对复合材料的协效阻燃抑烟作用及力学性能的影响。结果表明,在锥形量热实验中,热释放速率峰值相对减少42.8%,平均热释放速率和总热释放量相对减少29.5%和25.7%,总烟释放量相对降低了12.2%,一氧化碳平均产率相对降低了42.0%;扫描电子显微镜分析发现,APP具有催化成炭并形成膨胀泡沫炭层的作用,而SEP具有吸附聚集诱导成炭的作用;APP的阻燃机理主要属于气相阻燃机理,SEP的阻燃机理主要属于凝聚相阻燃机理;弯曲性能测试结果表明,SEP与APP对PVC/竹粉复合材料具有协同颗粒增强作用;拉伸性能测试结果表明,SEP对PVC/竹粉复合材料的塑性变形能力的损害比APP小。因此,SEP与APP联用能够对PVC/竹粉复合材料进行有效的阻燃抑烟,同时也能增强复合材料的力学性能。     

协同效应对环氧封端聚氨酯柔性树脂室温粘接性能的影响

采用自制环氧封端聚氨酯柔性树脂分别与三缩水甘油异氰尿酸酯(TGIC)和四缩水甘油基-4,4-二氨基二苯醚(TGDDE)混合配比,并用间苯二甲胺(MXDA)和聚醚胺(D-230)作为混合固化剂固化,研究不同官能度环氧的的协同作用对环氧封端聚氨酯柔性树脂室温粘接性能的影响.研究结果显示,三缩水甘油异氰尿酸酯的引入能有效地增...     

介孔SiO_2的有机化修饰及其对环氧树脂拉伸性能的影响

利用正硅酸乙酯(TEOS)及γ-氨基丙基三甲氧基硅烷(APTMS)共缩聚合成了蠕虫状的介孔二氧化硅(Si O2);研究了有机化修饰对介孔Si O2结构的影响;采用熔融共混法制备了环氧树脂/介孔Si O2复合材料,并研究了复合材料的拉伸性能。结果表明,APTMS的引入使介孔Si O2的有序性变差,孔径、孔容及比表面积减小,当介孔Si O2中APTMS的含量达到20%时,介孔结构消失;当介孔Si O2的用量为2%～10%时,环氧树脂/介孔Si O2复合材料的拉伸强度和断裂韧性提高较为显著,但断裂伸长率变化不大。     

高分子粘结膜与金属化合物对PVC树脂的协同阻燃消烟作用

研究了铝塑复合板中高分子粘结膜与Mg(OH)_2和CaCO_3复合阻燃剂对PVC树脂的协同阻燃消烟作用。通过NBS烟箱等仪器测试的有关参数对PVC体系中的金属化合物及填料的抑烟、阻燃效果进行了分析和研究。结果表明：在高分子粘结膜和金属化合物协同作用下能使烟密度(MSD)和生烟速率显著降低,而且有效地推迟了发烟时间。各种金属化合物对PVC体系的氧指数(LOI)影响不大,对烟密度的影响差异很大。     

Synergistic Effect of Epoxy/Organophilic Montorillonite Nanocomposites and Triphenyl Phosphate on Flame Retardance Enhancement of Polypropylene

Epoxy/organophilic montorillonite (Epoxy/OMMT) nanocomposites were prepared by epoxy intercalated into the interlayer of OMMT, and flame retardant polypropylene (PP) was obtained with Epoxy/OMMT nanocomposites and triphenyl phosphate (TPP) mixture as flame retardant agent. The effect of epoxy sorts, mass ratio of OMMT and Epoxy, and the contents of Epoxy/OMMT and TPP on properties of PP were studied. It was found that there is a remarkable synergistic flame retardant effect of novolac epoxy/organophilic montorillonite (NE/OMMT) and TPP on PP. Flame retardant PP with oxygen index (OI) value of 36.5%, peak heat release rate (PHRR) of 654 kW/m², notched Izod impact strength of 6.93 kJ/m² and tensile strength of 30.56 MPa was obtained when the mass ratio of OMMT and NE is 5:100, the content of NE/OMMT and TPP is 13.33 and 6.67 wt.%, respectively. The materials were characterized via X-Ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectrum (FT-IR), and thermogravimetry (TG). The XRD results and TEM photograph indicate OMMT is exfoliated in PP matrix when the mass ratio of OMMT and NE is lower than 10:100. The TG results show the evaporation of TPP is greatly hampered by NE/OMMT nanocomposite. PP with NE/OMMT-TPP has an onset weight loss temperature 31.7°C higher than PP with NE-TPP because of the shielding effect of OMMT layers. The FT-IR spectra indicate phosphoric acid is generated from TPP and carboxylic acid and phenyl ether are generated from NE under thermal degradation, which further results in the formation of thermally stable char. This charring process is also affirmed by the wide thermally stable zone at 380–550°C in TG curves of PP with NE/OMMT-TPP or NE-TPP.     

紫外老化对芳纶／环氧复合材料性能和结构的影响

通过紫外老化试验（温度（40±5）℃,湿度40％）,研究了芳纶、环氧及其复合材料的力学性能、玻璃化转变温度、失重随老化时间的变化,并用红外光谱分析了芳纶的结构变化。结果表明：经紫外老化后,芳纶／环氧的拉伸强度、失重率有明显的变化,芳纶结构和复合材料的玻璃化转变温度无明显的变化。     

MoO3/ZnO/APP对硬质PVC抑烟阻燃性能的影响

通过均匀实验设计方法研究了MoO3/ZnO/APP（聚磷酸铵）三元复合抑烟阻燃体系对硬质PVC复合材料的抑烟阻燃性能、力学性能和热稳定性的影响,用SPSS软件对试验结果进行了回归分析。结果表明,当MoO3、ZnO、APP分别为2.5份、3.5份和9份时,复合材料的协同抑烟阻燃性能最好,最大烟密度（SMD）由100降低到77.5,烟密度等级（SDR）由85.3降低到57.4,极限氧指数由44.5%提高到65.0%。复合材料的力学性能略有下降,拉伸强度由36.3MPa降至33.7MPa,断裂伸长率由48.1%降至44.7%。热重分析表明,MoO3/ZnO/APP三元复合抑烟阻燃体系使硬PVC失重温度范围变窄,最大失重温度降低了近50℃,而失重速率明显降低。     

Synergistic Effect of Magnesium Hydroxystannate with Intumescent Flame Retardants on Thermal and Fire Safety Properties of Polypropylene

Magnesium hydroxystannate [MgSn(OH)₆, MgHS] was successfully prepared by a facile coprecipitation method. Then, MgHS was used to intumescent flame-retardant polypropylene systems. Thermogravimetry analysis results indicated that the introduction of MgHS can improve the thermal stability of the intumescent flame-retardant polypropylene system. Limiting oxygen index and UL-94 vertical burning test data show that the addition of MgHS can significantly improve the flame retardancy of intumescent flame-retardant polypropylene system. From the cone calorimetry results, it can be observed that the peak heat release rate is decreased in comparison with intumescent flame-retardant polypropylene. Moreover, the addition of MgHS significantly reduced the gaseous products, especially carbon monoxide.