Thermal properties and combustion behavior of POSS‐ and bohemite‐finished cotton fabrics

A finishing process with polyhedral oligomeric silsesquioxane (POSS) and bohemite nanoparticles has been exploited for enhancing the thermal stability and flame retardancy of cotton fabrics. The thermal behavior of flame retardant treated cellulosic fabric has been studied by thermogravimetric analyses (TGAs). It has been found that such nanoparticles favor the carbonization of the cellulose and slow down the kinetics of thermo‐oxidation in air. At the same time, the finished fabrics have turned out to be more efficient with respect to neat cotton as far as the flame retardancy is concerned, pointing out an increase of the time to ignition (TTI) and a decrease of the heat release rate (HRR). Furthermore, a comparison between the fire performances of the nanoparticles under study and a commercial phosphorus‐based flame retardant has been investigated. The morphology and elemental composition present in the treated fabrics have been also investigated using scanning electron microscopy (SEM) coupled to the energy dispersive spectroscopy (EDS), and the results have been compared with the untreated fabric. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

聚合物／碳纳米管纳米复合材料的制备、热稳定性及阻燃性

综述了聚合物/碳纳米管(CNT)纳米复合材料3年多来(2003—2006)的研究进展,包括其制备方法、热稳定性及阻燃性,重点是其阻燃性(释热速率、质量损失速率、引燃时间、极限氧指数及UL94阻燃性等)。还详细论述了含多层碳纳米管(MWCNT)聚合物热裂及燃烧时的成炭情况和炭层结构及其作为复合材料阻燃剂与层状硅酸盐的异同。     

含磷本质阻燃高聚物研究进展

本质阻燃高聚物阻燃效能持久,不存在挥发、溶出及迁移的问题,且可实现分子内协同阻燃效应,又为环境兼容,故近年日益崭露头角。文中综述了这方面的一些最新研究进展,包括本质阻燃环氧树脂、聚酰胺、聚酰亚胺及聚氨酯等,它们均为分子主链或侧链带含磷基团的无卤型高聚物。文中主要介绍了其合成方法及性能。     

Effects of ageing on the fire behaviour of flame‐retarded polymers: a review

The influence of environmental ageing on the reaction to fire of flame‐retarded polymers is reviewed. Six types of stimuli have been identified as the most relevant parameters inducing fire behaviour modification: temperature, moisture, UV radiation, ionizing radiation, chemical solvent and physical stress. This review provides a state of the art and current comprehension of the effects of ageing on flame retardancy of polymers. Various physical and chemical phenomena lead to ageing and deterioration (or sometimes improvement) of the flame retardancy of polymers: release of additives (not only flame retardants) through thermal migration, solubilization, abrasion, etc., chemical degradation of the flame‐retardant system, and chemical or physical modification of the polymer structure (chain scission, crosslinking, diffusion of water, etc.). Obviously, ageing effects strongly depend on the material and the ageing scenario considered. Solutions to maintain flame‐retardant efficiency in aggressive conditions are also presented. © 2014 Society of Chemical Industry     

碳酸钙对乙烯-丙烯酸丁酯共聚物阻燃与力学性能及热降解行为影响研究

采用极限氧指数法、热重分析和差示扫描量热分析等研究了碳酸钙（CaCO3）对乙烯-丙烯酸丁酯共聚物（EBA）阻燃及热降解行为的影响，探讨了CaCO3对EBA力学性能和熔体流动速率的影响。结果表明，CaCO3降低了EBA的拉伸强度、断裂伸长率和熔体流动速率，但复合阻燃材料仍具有良好的加工性能；当CaoCO3含量为60％（质量分数，下同）时，阻燃材料的极限氧指数可达28．5％。CaCO3通过EBA在热降解过程中与之发生化学反应来改变EBA的热降解行为，提高在高温下的热稳定性，降低EBA的热降解速率，促进高温下成炭在凝缩相中发挥阻燃作用。此外，CaCO3与EBA在热降解过程中形成隔热、隔氧的多孔泡沫膨胀结构，可进一步加强阻燃效果。     

Seaweed as novel biofiller in polypropylene composites

Based on former exploratory research, we used seaweed (SW) fiber as a novel biofiller for the production of polypropylene (PP) biocomposites. Maleic anhydride‐grafted polypropylene (MAPP) and a CNT masterbatch (CESA) were applied as compatibilizers. Mechanical properties, crystallization behavior, dynamic mechanical performance as well as interfacial morphology were characterized. SW fiber was successfully incorporated in the PP matrix in terms of mechanical reinforcement. Accelerated crystallization process of PP matrix was observed. DMA results also indicated the favorable adhesion between SW fiber and PP matrix, which could be confirmed by SEM characterization. The effect and efficiency of MAPP and CESA as compatibilizers were evaluated. Moreover, potential flame retardancy of SW fibers for PP matrix was observed, and satisfying results warrant further investigations. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Characterization of a novel silicon-containing hybrid polymer by thermal curing,pyrolysis behavior,and fluorescence analysis

A novel linear silicon-containing hybrid polymer with C  C and Si H linkages, diphenyl-dihydroethynyl-silane (DPHES), had been conveniently synthesized and well characterized. The thermal curing, crosslinked structure and pyrolysis behavior were studied by DSC, Fourier transform infrared (FTIR), and Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The results suggest the crosslinked structures consist mainly of phenyl and aromatic fused rings, which are formed through cyclotrimerization, addition reaction, and hydrosilylation reaction. The thermal properties indicate that the crosslinked DPHES exhibits excellent thermal stability with the temperature at 5% weight loss are higher than 572 and 509 °C under nitrogen and air atmosphere, respectively. The fluorescence emission spectra show DPHES and its crosslinked product also have moderate fluorescence properties, emitting purple light, and visible blue light, respectively, which further verified the structure of DPHES. These results suggest that DPHES has the potential to be used as light-emitting materials with excellent thermal properties. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47403.     

Synthesis,curing behavior and thermal properties of silicon‐containing hybrid polymers with Si−C≡C units

Three novel kinds of linear silicon‐containing hybrid polymers with Si?C≡C units were synthesized by polycondensation reactions using the Grignard reagent method. All the polymers were thermosetting, highly heat‐resistant, moldable and easily soluble in common organic solvents. The structure, curing behavior, thermal and oxidative properties were characterized using Fourier transform infrared spectroscopy, ¹H NMR, ¹³C NMR, gel permeation chromatography, differential scanning calorimetry and thermogravimetric analysis. The results obtained can provide theoretical guidance for determining the curing of the resin system. In addition, the cured polymers exhibit excellent thermal and oxidative stabilities with temperatures of 5% weight loss (T_d5) above 480 °C and 450 °C in nitrogen and air respectively; the residues at 1000 °C were above 70.0% and 45.0% respectively. The thermal and oxidative stabilities of the polymers are attributed to a crosslinking reaction between the Si?H and C≡C bonds or C≡C bonds. These polymers have the potential for use as high‐temperature‐resistant resins and ceramic precursors. © 2013 Society of Chemical Industry     

Thermal degradation behaviors of polypropylene with novel silicon‐containing intumescent flame retardant

The N‐[3‐(dimethoxy‐methyl‐silanyl)‐propyl]‐N′‐ (9‐methyl‐3,9‐dioxo‐2,4,8,10‐tetraoxa‐3,9‐diphospha‐spiro[5.5]undec‐3‐yl)‐ethane‐1,2‐diamine/dimethoxy dimethyl silane copolymer (PSiN II), which simultaneously contains silicon, phosphorus, and nitrogen, is synthesized and incorporated into polypropylene (PP). The flame retardancy is evaluated by the limiting oxygen index value, which is enhanced to 29.5 from 17.4 with 20% total loading of PSiN II. The thermal degradation behavior of PP/PSiN II is investigated by thermogravimetric analysis under N₂ and air. The PP/PSiN II sample degrades at 400°C for different amounts of time, and the process of degradation is studied by Fourier transform IR. The morphology of the char formed at 400°C for 10 min is investigated by scanning electron microscopy. The swollen inner structure, close, and smooth outer surface provide a much better barrier for the transfer of heat and mass during fire and good flame retardancy. The thermal stability of PP is improved by incorporation of PSiN II. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2487–2492, 2005     

Influence of fullerenes on the thermal and flame-retardant properties of polymeric materials

At present, the application of fullerene in polymer materials has become an attractive issue. Fullerene can enhance the thermal and flame-retardant properties of polymers due to its high capacity to trap free radicals. Fullerene also has good synergistic effect with inorganic metal flame retardant, intumescent flame retardant, brominated flame retardant (BFR), clay, carbon nanotubes, graphene oxide, and so on. In this review, the impact and mechanism of fullerene and its derivatives on the thermal and flame-retardant properties of polymeric materials are discussed. And the prospect of fullerene in flame-retardant polymer composites is also briefly introduced by analyzing the research progress in the recent years. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 47538.     

Thermal degradation behavior of epoxy resin blended with propyl ester phosphazene

The study was focused on the thermal degradation behavior of epoxy resins (EP) blended with propyl ester phosphazene (FR). The analysis studied the evolved gas and the residual char yield using different techniques. The results showed that pure epoxy resin and their blends were all a one‐stage thermal degradation reaction. The major degradation temperature of blends was lower than the temperature of pure epoxy resin, but the residual char yield of epoxy blends at 550°C was higher than that of pure epoxy resin. FR could accelerate the production of small molecules such as acetone, phenol, and isopropyl phenol during thermal degradation process. Honeycomb structure compounds were also formed in the residual char of epoxy and its blends. Additionally, elemental analysis of the residual char yield showed that phosphorus was a residual element, and other elements mostly diffused to the evolved gas. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1161–1174, 2001     

PFF与PUF热稳定性及燃烧性能研究

制备了酚醛泡沫和聚氨酯泡沫，并研究了酚醛硬泡与聚氨酯硬泡的热稳定性及燃烧性能。结果表明：和聚氨酯泡沫比较，酚醛泡沫的热失重小，热释放速率和热释放总量低。因此酚醛泡沫的热稳定性和阻燃性能明显优于聚氨酯泡沫。     

聚氨酯/改性蒙脱土纳米复合材料的热稳定性及阻燃性

综述了近年聚氨酯/改性蒙脱土纳米复合材料的热稳定性及阻燃性的研究进展,包括材料的制备方法、热稳定性(热分解温度及热失重)、阻燃性(氧指数、释热速率、火灾性能指数与质量损失速率)及的蒙脱土改性材料与常规阻燃剂(磷酸酯(盐))的阻燃协效作用。     

溴/氮本质阻燃环氧树脂的热性能和阻燃性能研究

采用热分析仪、傅里叶变换红外光谱仪(FTIR)、极限氧指数仪和综合垂直燃烧测定仪研究了反应型磷/氮阻燃剂聚N-(2,3,5,6-四溴对二亚甲基苯基)-N-乙基胺(BNFR)阻燃环氧树脂的热性能、阻燃性能、成烟性能等。结果表明,BNFR分子通过参与固化反应而以化学键键合于固化树脂的立体网络结构之中,无迁移,通过改变固化树脂的热降解过程提高树脂的热稳定性能以及阻燃性能;BNFR分子结构中含有Br和N两种阻燃元素,气相和固相阻燃机理同时起作用,因此阻燃效率较高,环氧树脂中添加12%的BNFR可以使极限氧指数达到30%,600℃成炭量高于10%。     

新型含磷酚醛树脂的合成与性能

通过亚膦酸酯与碳碳双键之间的亲电加成反应,合成了一种新型的含磷马来酰亚胺酚醛树脂。采用红外光谱(FTIR)和元素分析法对聚合物的结构进行了表征。并用此含磷酚醛树脂作为环氧树脂的固化剂制得了一含磷氮的环氧固化物。采用热分析法、极限氧指数法对相应环氧固化物的耐热性能和阻燃性能进行了表征。研究结果表明:以该含磷聚合物作为环氧树脂的固化剂,对稳定固化物骨架碳的结构和交联成炭能力的提高起到了增强作用;环氧固化物具有较高的玻璃化转变温度(145.4℃)和较高的热稳定性(T508℃),极限氧指数显示其具有较好的阻燃性能。     

Synthesis of novel phosphorus-containing epoxy hardeners and thermal stability and flame-retardant properties of cured products

Two novel flame-retardant curing agents for epoxy resins, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)-containing 4-[(phenylamino)methyl]phenol (P-Ph) and DOPO-containing Mannich-type bases (P-DDS-Ph), were synthesized by the condensation of 4-hydroxybenzaldehyde with 4-aminophenol and DDS, respectively, followed by the addition of DOPO to the resulting imine linkage. Chemical structures of these materials were characterized with FTIR, ¹H-NMR spectra, ³¹P-NMR spectra, and elemental analysis. The thermal properties and flame retardancy of o-cresol novolac epoxy resin (CNE) cured with different contents of the phosphorus-containing compounds were investigated by nonisothermal differential scanning calorimetry, thermogravimetric analysis, and limiting oxygen index (LOI). The obtained results showed that more char was formed while containing lower contents of the phosphorus-containing compounds in the P-Ph/CNE and P-DDS-Ph/CNE indicating their excellent flame retardancy. Moreover, the P-DDS-Ph/CNE exhibited higher T_g (224°C) and better thermal stability (T_10%, 330°C) than that of P-Ph/CNE. Therefore, the developed P-DDS-Ph/CNE may be potentially used as environmentally preferable products in electronic fields. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

建筑幕墙用阻燃型硅酮密封胶的热性能

以107硅橡胶交联季铵盐改性硅油为基体,聚磷酸铵和高硼硼酸钙为复合阻燃剂,制备了阻燃型硅酮密封胶,研究了其阻燃性能、热分解动力学、耐热氧化降解性能、分子结构尺寸稳定性.结果表明:107硅橡胶含量为60％(w),阻燃剂添加量为9％(w)时,阻燃型硅酮密封胶的点燃时间为48?s,总燃烧时间为397?s,最大热释放速率较无阻...     

Thermal degradation and combustion behavior of intumescent flame‐retardant polypropylene with novel phosphorus‐based flame retardants

The objective of this study was to develop an environmentally friendly fire‐retardant polypropylene (PP) with significantly improved fire‐retardancy performance with a novel flame‐retardant (FR) system. The system was composed of ammonium polyphosphate (APP), melamine (MEL), and novel phosphorus‐based FRs. Because of the synergistic FR effects among the three FRs, the FR PP composites achieved a V‐0 classification, and the limiting oxygen index reached as high as 36.5%. In the cone calorimeter test, both the peak heat‐release rate (pHRR) and total heat release (THR) of the FR PP composites were remarkably reduced by the incorporation of the novel FR system. The FR mechanism of the MEL–APP–FR–PP composites was investigated through thermogravimetric analysis and char residue characterization, and the results reveal that the addition of MEL–APP–FRs promoted the formation of stable intumescent char layers. This led to the reduction of pHRR and THR and resulted in the improvement of the fire retardancy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45962.     

IFR/SiO2和IFR/MgSiO3协效阻燃TPU材料的性能比较

以三嗪成炭发泡剂（CFA）及聚磷酸铵（APP）复配成膨胀阻燃剂(IFR),以二氧化硅(SiO2)及硅酸镁(MgSiO3)为协效剂制备阻燃TPU材料,对比研究了2种热塑性聚氨酯弹性体（TPU）材料的阻燃性能、力学性能、热降解行为、炭层的表面形貌及表面元素组成。结果表明,当IFR总添加量为30 %（质量分数,下同）,SiO2占IFR的5 %时,1.6 mm样条在燃烧时产生大量熔滴,材料通过UL 94 V-2级,极限氧指数（LOI）为39.5 %,而当阻燃剂总添加量为26 %,MgSiO3占IFR的5 %时,1.6 mm样条在燃烧时无滴落,材料通过UL 94 V-0级,LOI为35.7 %,表明MgSiO3在该阻燃体系中具有很好的抑制熔滴的作用;与添加SiO2相比,MgSiO3的加入对材料拉伸性能的影响更小;MgSiO3的加入使得炭层中磷元素含量明显增加;MgSiO3的加入使得阻燃TPU材料在燃烧时产生了更加连续、致密且具有良好强度的炭层,对内部材料起到了更好的保护作用,从而提高了材料的阻燃性能。     

S–N–P阻燃剂对聚碳酸酯热分解与老化寿命的影响

采用热重(TG)分析法研究了不同升温速率下,S–N–P阻燃剂对聚碳酸酯(PC)热分解过程的影响。结果表明,S–N–P阻燃剂的加入使PC的初始分解温度和失重速率最大时的温度降低,即S-N-P阻燃剂能促进PC提前分解成炭。通过Kissinger和Flynn-Wall-Ozawa法对其热分解动力学进行了探讨,两种方法计算结果均表明S–N–P阻燃剂的加入使得PC的热分解活化能降低。采用时–温等效原理对阻燃PC老化寿命进行了预估,发现S–N–P阻燃剂的加入使PC老化寿命明显缩短,但也表明S–N–P阻燃剂加速了PC降解成炭的过程,从而更好地提高了PC的阻燃性能。