NaOH和Na2SiO3对纤维板阻燃性能的比较研究

通过对比在纤维板表面涂覆NaOH和Na2SiO3溶液,基于小室燃烧法、垂直燃烧仪和极限氧指数等研究其阻燃性能.结果表明,表面改性纤维板的阻燃性能排序为:涂Na2SiO3纤维板>涂NaOH+Na2SiO3纤维板>涂NaOH纤维板>未处理纤维板>泡水处理纤维板,单面涂覆的阻燃性能优于双面涂覆,极限氧指数可达25.2%.提出了NaOH与Na2SiO3对中密度纤维板的阻燃机理,涂覆NaOH溶液易使纤维板的阻燃物质迁移至表面,掺入的Na2SiO3可在纤维板表面形成含(=)Si-O-Si(=)链的三维网状硅质层,进而提高其阻燃性能.     

A formaldehyde‐free flame retardant wood particleboard system based on two‐component polyurethane adhesive

To address the problem of formaldehyde‐free flame retardation of wood particleboard, a novel phosphorus‐containing compound, di(2,2‐dimethyl‐1,3‐propanediol phosphate) urea (DDPPU) was synthesized. DDPPU was used as flame retardant for wood particleboard. The flammability of treated wood particleboard systems consisted of wood particles, polyurethane (PU) adhesive, and different flame retardant formulations were investigated by limiting oxygen index (LOI). The results of LOI indicate that DDPPU could improve the flame retardancy of wood particleboard. However, when H₃BO₃ was used as the second flame retardant component and combined with DDPPU, the flame retardant wood particleboard could obtain the highest LOI value (46.0) in these experiments. Thermogravimetric analysis shows that treated wood particleboard can decrease the initial decomposition temperature, and that at higher temperatures the degradation rate are lower than the untreated wood particleboard. Furthermore, wood particleboard treated with DDPPU/H₃BO₃ has a higher yield of residue char at 600°C than that treated with other flame retardant systems. The ability of char formation of these samples agrees with the order of LOI values. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and Application of Hexaallylamino-cyclo-triphosphazene as Flame Retardant in Latex Coatings

The paper deals with a novel flame retardant and its application in waterborne coatings. The flame retardant was synthesized from hexachloro-cyclo-triphosphazene by nucleophilic substitution with allylamine. Functionalized emulsion copolymers bearing in the structure hexaallylamino-cyclo-triphosphazene were prepared by the semicontinuous emulsion polymerization. The latexes were used as the main component of transparent coating systems cured by melamine formaldehyde resin. The incorporation hexaallylamino-cyclo-triphosphazene did not affect transparency, flexibility, and toughness of resulting coatings and increased their flame stability in terms of the amount of smoke release and maximum average rate of heat emission indicating a slower flame spread during the material combustion.     

阻燃高回弹聚氨酯泡沫的挥发性研究

使用含氮结构型阻燃聚脲多元醇对阻燃高回弹聚氨酯泡沫的挥发性进行了研究．考察了配方中聚脲多元醇、催化剂、泡沫稳定剂、阻燃剂对泡沫挥发性的影响。研究结果表明,使用聚脲多元醇、反应型催化剂、低挥发性泡沫稳定剂生产的阻燃高回弹聚氨酯软泡较普通阻燃高回弹聚氨酯软泡具有较低的VOC（挥发性有机物）、甲醛释放量和雾化值。     

Development of a DOPO‐containing melamine epoxy hardeners and its thermal and flame‐retardant properties of cured products

In this study, a novel Schiff base of melamine used as flame‐retardant curing agent for epoxy resins, was synthesized via condensation reaction of 4‐hydroxybenzaldehyde with melamine, followed by the addition of 9,10‐dihydro‐9‐oxa‐10‐phosphaphen‐anthrene 10‐oxide (DOPO) to the resulting imine linkage. The structure of DOPO‐containing melamine Schiff base (P‐MSB) was characterized by Fourier transformed infrared spectroscopy, ¹H‐nuclear magnetic resonance (¹H‐NMR) and ³¹P‐NMR. The compound (P‐MSB) was used as a reactive flame retardant in o‐cresol formaldehyde novolac epoxy resin (CNE) to prepare flame‐retardant epoxy resins for electronic application. The thermal and flame‐retardant properties of the epoxy resins cured by various equivalent ratios phenol formaldehyde novolac (PN) and P‐MSB were investigated by the nonisothermal differential scanning calorimetry, the thermogravimetric analysis, and limiting oxygen index test. The obtained results showed that the cured epoxy resins possessed high T_g (165°C) and good thermal stability (T_5%, 321°C). Moreover, the P‐MSB/CNE systems exhibited higher limiting oxygen index (35) and more char was maintained in P‐MSB/CNE systems than that in PN/CNE system and the effective synergism of phosphorus–nitrogen indicated their excellent flame retardancy. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and properties of novel phosphorus‐containing hardener for epoxy resins

A novel phosphorus‐containing curing agent, 2‐(6‐oxid‐6H‐dibenz〈c,e〉〈1,2〉oxa‐phosphorin‐6‐yl) phenol formaldehyde novolac [OD‐PN], was prepared from phenol formaldehyde novolac resin (PN) and a reactive 2‐(6‐oxid‐6H‐dibenz〈c,e〉〈1,2〉oxa‐phosphorin‐6‐yl)chloride (ODC) while ODC was synthesized through reaction between o‐phenylphenol and phosphoryl trichloride. The compound (OD‐PN) was used as a reactive flame‐retardant in o‐cresol formaldehyde novolac epoxy resin (CNE) for electronic application. Owing to the rigid structure of ODC and pendant P group, the resulted phosphorus containing epoxy resin exhibited better flame retardancy, higher glass transition temperature, and thermal stability than the noncyclic P‐containing curing agent or the bromine containing flame‐retardant epoxy resin. UL 94‐VO rating could be achieved with a phosphorus content of as low as 1.21% (comparable to bromine content of 6%) in the cured resin, and no fumes and toxic gas emission were observed. The relationship between the structure and flammability for both phosphorus containing curing agents OD‐PN and TP‐PN (triphenyl phosphate‐phenol formaldehyde novolac reaction product) are also examined. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1636–1644, 2000     

Synergistic action of Sb2O3 with bromine-containing flame retardant in polyolefins: 3—The relationship between certain combustion variables

The combustion of polypropylene flame-retarded by the synergistic action between Sb₂O₃ and bromine-containing flame retardants has been studied. From the relationship between a number of the variables, a parameter quantatively reflecting the flame retardant effect has been found. With the addition of flame retardant, the rate of weight loss, the CO and CO₂ emission rates and heat release all decrease while smoke density increases. These effects were considered to depend on the concentration of HBr gas in the pyrolysates released into the gas phase (i.e., dW_HBr/dW, HBr flux ensity), and the following equations were obtained: η*(dW/dt)_max, which approximately corresponds to the oxidation velocity of pyrolized hydrocarbon, is inversely proportional to the HBr flux density. As the conversion of CO to CO₂ was almost independent of the amount of flame retardants added, the flame retardant effect of bromine-containing flame retardants was considered to be a retardant effect of the initial oxidation reaction at the gas liquid interface. Moreover, η* is almost proportional to the combustion efficiency η, which was obtained from the heat release measured in the flaming region. The heat release is therefore considered to be governed by the HBr flux density.     

Flame‐retardant finishing in cotton fabrics using zinc oxide co‐catalyst

In this article, N‐Methylol dimethylphosphonopropionamide (FR) in combination with a melamine resin (CL), phosphoric acid (PA) catalyst and zinc oxide (ZnO) or nano‐ZnO co‐catalyst were used (FR‐CL‐PA‐ZnO or nano‐ZnO system) to impart flame‐retardant property on cotton fabrics. FR‐CL or FR‐CL‐PA‐treated cotton specimen showed roughened and wrinkled fabric surface morphology, which was caused by the attack of the FR with slightly acidity. In addition, FTIR analysis showed some new characteristic peaks, carbonyl, CH₂ rocking and CH₃ asymmetric and CH₂ symmetric stretching bands, in the chemical structure of treated cotton specimens. Apart from these, the flame ignited on the flame‐retardant‐treated fabrics (without subjected to any post‐wet treatment) extinguished right after the removal of ignition source. However, FR‐CL treated specimens were no longer flame‐resistant when the specimens subjected to neutralization and/or home laundering, while FR‐CL‐PA treated specimens showed opposite results. By using 0.2% and 0.4% of ZnO or nano‐ZnO as co‐catalyst, the flame spread rate of neutralized and/or laundered test specimens decreased, even the specimens were undergone 10 home laundering cycles. Moreover, flame‐retardant‐treated cotton specimens had low breaking load and tearing strength resulting from side effects of the crosslinking agent used, while addition of ZnO or nano‐ZnO co‐catalyst could compensates for the reduction. Furthermore, the free formaldehyde content was dropped when ZnO and nano‐ZnO co‐catalyst was added in the treatment. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Emission characteristics of methanol combustion in constant volume spherical vessels

Emission characteristics of methanol combustion were studied by means of constant volume combustion in spherical vessels, the crevice volume of which was minimized as much as possible. CO, unburnt methanol (UBM), formaldehyde and NO_x were important primary emission species from the environmental viewpoint. The yields of these emissions were measured as functions of equivalence ratio ?. CO and NO_x emissions corresponded to calculated equilibrium compositions at the adiabatic flame temperatures. On the other hand, UBM and formaldehyde were not predicted. UBM had a minimum value at ? ≈ 1.1. UBM and formaldehyde emissions were pressure-dependent, indicating that these emissions were related to quenching phenomena. By employing a larger vessel with a smaller surface/ volume ratio, these emissions could be reduced considerably. Methyl nitrite was produced as an important emission species via post-combustion reactions between UBM and NO_x. Water addition was found not to affect the emission characteristics seriously.     

Preparation and properties of composites based on melamine‐formaldehyde foam and nano‐Fe3O4

In this work, a novel melamine‐formaldehyde‐Fe₃O₄ foam was prepared from a mixture containing melamine‐ethanolamine‐formaldehyde resin, melamine‐glycol‐formaldehyde resin and carboxylated Fe₃O₄ nanoparticles by microwave foaming method. The two resins were characterized by ¹³C‐NMR, respectively. The structures of foams, mechanical and fire‐retardant properties were experimentally characterized separately by scanning electron microscopy, universal testing machine, limit oxygen index, thermogravimetry‐differential thermal analysis, and Fourier transform infrared spectra. The effects of the resin viscosity, emulsifier, nucleating agent, curing agent, silicone oil, microwave heating time and blowing agent on the structure of foam were investigated. Results showed that the properties of foam were decided by not only the molecular structure but also structure of foam, and the carboxylated Fe₃O₄ nanoparticles can improve the toughness and flame retardant properties of magnetic foam obviously from both aspects. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2688–2697, 2013     

纤维板用胶粘剂及其甲醛释放量的研究新进展

介绍了醛类胶粘剂型、低/无甲醛胶粘剂型、无胶粘剂型纤维板的研究状况;重点阐述了改性脲醛树脂胶在纤维板中的应用、游离甲醛的产生机理及检测方法、减少纤维板中游离甲醛释放量的有效方法.     

无卤阻燃聚丙烯的制备与性能研究

通过熔融复合工艺,对聚丙烯(PP)进行阻燃和增韧改性。使用膨胀型阻燃剂(由聚磷酸铵(APP)与季戊四醇(PER)组成)为主阻燃剂,在此基础上研究了4A分子筛对阻燃体系的力学性能、阻燃性能及流变性能等的影响;在PP阻燃体系中加入三元乙丙橡胶(EPDM),探讨了EPDM对PP阻燃体系力学性能和阻燃性能的影响。结果表明:4A分子筛用量为2%、EPDM用量为6%时,阻燃体系的综合性能最佳。     

A novel blowing agent polyelectrolyte for fabricating intumescent multilayer coating that retards fire on cotton fabric

Sulfonated melamine‐formaldehyde (SMF) resin was successfully synthesized with a mixture of formaldehyde, melamine, and NaHSO₃ in an aqueous solution. Then the SMF was used as the blowing agent to combine with chitosan and phytic acid for fabricating the intumescent flame retardant coating on the surface of the cotton fabric by layer‐by‐layer (LbL) self‐assembled technology. As characterized by X‐ray photoelectron spectroscopy, scanning electron microscopy, and attenuated total reflection Fourier transform infrared spectroscopy, the (chitosan/SMF + phytic acid)_n coating was successfully deposited on the surfaces of cotton fibers. Thermogravimetric analysis results exhibited that the thermal stabilities of coated cotton fabrics under nitrogen and air atmosphere were enhanced at temperatures ranging from 400 to 700 °C compared with pure cotton fabric. At 700 °C, the char residues of cotton‐5BL and cotton‐10BL under a nitrogen atmosphere were improved 25.9 and 32 wt % than that of pure cotton fabric, respectively. In the vertical flame test, the self‐extinguishing could be obtained for the cotton‐10BL sample. This work first utilized SMF as negative polyelectrolyte to fabricate intumescent flame retardant coating by LbL self‐assembled technology on cotton fabric to strengthen its thermal stability and flame resistance. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46583.     

Flame retardant,mechanical, and hot air aging properties of ethylene-propylene-diene monomer/ammonium polyphosphate/nano-silic composite rubber

In this work, effect of the ratio of nonhalogenated flame retardants (ammonium polyphosphate [APP] and nano-silica [nano-SiO₂]) on the mechanical, thermal, and flame retardant properties of ethylene-propylene-diene monomer (EPDM) composite rubber were investigated. Vulcanization characteristics, high temperature compression permanent deformation, thermal oxygen aging, dynamic thermodynamic analysis, thermal stability, cone calorimetry, limiting oxygen index (LOI), horizontal vertical combustion (UL-94), and scanning electron microscopy were carried out. The experimental results showed that the mechanical properties of the composite rubber decreased with the addition of APP. However, the addition of nano-SiO₂ was found to significantly improve the mechanical properties of the composite rubber when it was incorporated. In terms of flame retardant properties of EPDM composite rubber, the combination of APP and nano-SiO₂ has a synergistic flame retardant effect in comparison to the use of single APP flame retardant. The heat release rate of EPDM composite rubber decreased by 34%, the total heat release decreased by 19%, the LOI increased by 76%, and the flame retardant grade of EPDM composite rubber reached V-0. The EPDM composite rubber fabricated in the present study showed excellent fire resistance and desirable mechanical properties, which are of practical significance for further expanding the application ranges of EPDM rubbers.     

Decreasing formaldehyde emission from medium density fiberboard panels produced by adding different amine compounds to urea formaldehyde resin

In this study, medium density fiberboard panels were produced by adding different ratios of some amine compounds to urea formaldehyde resin, which had 1:1.17 mol ratios. The formaldehyde contents, physical, and mechanical properties of medium density fiberboard panels were determined according to EN standard methods.In this study, it was determined that the formaldehyde emission emitted from medium density fiberboard panels decreased by adding urea, propylamine, methylamine, ethylamine, and cyclopentylamine solution. It was found that the water absorption and thickness swelling values increased slightly; however, the internal bond strength, modulus of rupture, and modulus of elasticity of medium density fiberboard panels also increased substantially, but these properties of medium density fiberboard panels decreased by adding higher ratios of urea solution. It was found that the formaldehyde emission of medium density fiberboard panels decreased 16.5% by using a 16% rate of urea formaldehyde resin and 0.8% rate of urea and ethylamine solution. These decreases were determined as 57% for cyclopentylamine solution addition, 41% for propylamine solution addition, and 48% for methylamine solution addition.     

Thermal gasification behavior of plastics with flame retardant

In order to develop effective final treatment system of waste plastics, thermal gasification characteristics of plastics compounds containing flame retardant were investigated. Polypropylene (PP) with flame retardant, which was composed by Al(OH)₃ or (NH₄PO₃)_n, was decomposed in an image furnace. Mass reduction during thermal decomposition was measured by an electric micro-balance. The gas components produced by the thermal decomposition were analyzed with a gas analyzer (MEXA 4000 FT, Horiba Ltd.). Soluble organic fraction (SOF) components in a condensable emission during the decomposition process were analyzed with a combustion type PM analyzer (MEXA 1370 PM, Horiba Ltd.). In addition, SOF and solid carbon in the remains after the thermal decomposition were also analyzed by the PM analyzer. The oxygen concentration was changed from 0% to 21% and the content of flame retardant was changed from 0% to 50%. It was found that thermal decomposition temperature increased with a decrease of oxygen concentration. Flame retardant had small effect on the thermal decomposition temperature. However, gas components produced by thermal decomposition were changed corresponding to the containing ratio of flame retardant. The mass of remains was also affected by the ratio of flame retardant. As for the PP with Al(OH)₃, it was considered that PP was completely decomposed and main component of the remains was Al₂O₃ produced by decomposition of Al(OH)₃ even if the surrounding temperature increased up to 900 K. As for the PP with (NH₄PO₃)_n, gradual mass reductions continued after rapid mass reductions. The ratio of SOF and carbon contents in the remains after decomposition of PP with (NH₄PO₃)_n were higher than the case of PP with Al(OH)₃.     

分子筛在无卤膨胀阻燃体系中的协效催化作用

考察了分子筛在自制膨胀型阻燃体系(IFR)中的协效催化作用。利用添加分子筛的IFR对聚丙烯(PP)进行阻燃。运用扫描电子显微镜、垂直燃烧仪等对膨胀阻燃PP体系的表面形态和性能进行了研究。结果表明,阻燃PP加入不同的分子筛后,燃烧级数达到V-0级,氧指数最高增加17.86%,有明显的成炭效果,可获得良好的阻燃性能。     

The flammability of expandable polystyrene foams coated with melamine modified urea formaldehyde resin

Urea formaldehyde resin (UF) was modified by introducing melamine during the condensation in order to reduce the amount of free formaldehyde and increase the solid content. The melamine modified UF (MUF) was firstly mixed with intumescent flame retardant (IFR) and then coated on the surface of pre‐expanded polystyrene (PS) particles to prepare flame retardant expandable PS (EPS) foams. The flammability of EPS foam samples was characterized by limiting oxygen index (LOI), UL‐94 vertical burning and cone calorimeter tests, and the results indicated that the peak heat release rate was significantly reduced from 406 to 49 kW/m² and LOI value could reach 36.3 with V‐0 rating in UL‐94 test after coated with IFR. The smoke density test indicated that the maximum smoke density was decreased by the addition of IFR. Thermal analysis suggested that the thermal stability and char formation were significantly improved by the presence of coated flame retardants. The residual char observation revealed that MUF and IFR were beneficial to form integrated char layers with hollow stents, which could be the main reason for the improvement of flame retardant properties. The mechanical properties of flame retardant EPS foams can still meet the standard requirements for industrial applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44423.     

A hybrid intumescent fire retardant coating from cake- and eggshell-type IFRC

In this study the applicability of flame retardant mixed with a carbon source (such as pentaerythritol) for the intumescent fire retardant coating (IFRC) daubed on the top of a piece of plywood was investigated. There are three kinds of flame retardants used in this study: (1) artificial mesophase graphite powder (MGP), (2) sericite (Al₄(OH)₄(KAlSi₃O₁₀)₂), and (3) graphite. The desirable sizes of graphite, MGP and sericite were obtained by sieving. The graphite, MGP and sericite were characterized using a scanning electron microscope (SEM) and an energy dispersive spectrum (EDS). The IFRC, which consisted of 19.8% of flame retardant (or flame retardant mixed with carbon source), 15% of dehydrate agent, 18% of foaming agent, 7.2% of resin binder, and 40% of solvent, was prepared and daubed on the top of plywood. The fire protection capability of IFRC was tested using a flammability 45° tester. A conventional IFRC (with the carbon source) was also prepared to study the effect of adding the mixture of flame retardant and carbon source on the fire protection capability of IFRC. The microstructures of the conventional IFRC, the IFRC with flame retardant, and the hybrid IFRC (with flame retardant and carbon source) were inferred and demonstrated using SEM micrographs of the cross-section of three kinds of burnt IFRC. Most interestingly, the fire protection capability of the hybrid IFRC exceeds that of the conventional IFRC even though the percentage of carbon in the burnt hybrid IFRC is less than that in the burnt conventional IFRC.     

Effect of different acids during the synthesis of urea-formaldehyde adhesives and the mechanical properties of medium-density fiberboards bonded with them

The characteristics of urea-formaldehyde (UF) adhesives condensed by catalysis with four different acids, namely formic (HCOOH), hydrochloric (HCl), phosphoric (H₃PO₄), and sulfuric (H₂SO₄) acids, under alkaline–acidic–alkaline conditions at a molar ratio F/U = 1.12 were studied. The thermal curing properties of UF adhesives catalyzed with acid were characterized by differential scanning calorimetry at 10 °C/min heating rate. The resin structure examined by ¹³C-NMR spectroscopy showed that the resin catalyzed with HCl had a lower proportion of methylol groups, resulting in a lower level of formaldehyde emission. It was interesting to note that HCOOH resulted in the best overall mechanical properties of the medium-density fiberboard (MDF) panels. The HCl catalyst resulted in the poorest performance, providing the lowest internal bond strength, modulus of elasticity, and thickness swelling, with the exception of the free formaldehyde content. The resin catalyzed with H₂SO₄ had the highest free formaldehyde and the highest formaldehyde emission. H₂SO₄ and H₃PO₄ resulted in MDF mechanical properties relatively lower than for HCOOH. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47256.