软质聚氨酯泡沫塑料用无卤阻燃剂的研究

本文以羟基苯氧膦丙烯酸(CEPP)和三聚氰胺(MA)为原料合成了一种含磷、氮无卤阻燃剂(CMA),采用FT-IR表征了阻燃剂的化学结构,并将该阻燃剂用于软质聚氨酯泡沫(FPUF)的阻燃。用扫描电镜(SEM)研究了阻燃剂的加入对FPUF的形态的影响,通过LO I和垂直燃烧(Cal.117A)测试研究了该阻燃剂对FPUF的阻燃效果。结果表明,CMA可以有效提高FPUF的阻燃性:当CMA的添加量为10%时,FPUF即可通过Cal.117A测试,其LO I值也从17.3提高到23.0;随阻燃剂添加量的增加,FPUF的阻燃性能也逐渐提高。TG测试结果表明CMA的加入对FPUF的热稳定性没有多大影响。     

Effects of flame‐retardant ramie fiber on enhancing performance of the rigid polyurethane foams

Ramie fiber (RF) with excellent tensile strength was treated by a flame retardant and obtained the modified RF (MRF) that is incombustible. Then, MRF was used to improve the performance of rigid polyurethane foams (RPUF). The mechanical properties of the composite were investigated by compressive strength test and shear stress test. The fire characteristics were studied using a cone calorimeter. And the thermal decomposition and flammable properties were further evaluated using thermogravimetric analysis and limiting oxygen index. The results showed that MRF improve the mechanical properties of RPUF and eliminate the harm of flammability of RF on the RPUF.     

Bi‐phase flame‐retardant effect of dimethyl methylphosphonate and modified ammonium polyphosphate on rigid polyurethane foam

The flame‐retardant rigid polyurethane foams (RPUFs) with dimethyl methylphosphonate (DMMP) and modified ammonium polyphosphate (MAPP) were prepared. The results showed that the limiting oxygen index (LOI) value was improved by adding DMMP into RPUF/MAPP composite; 10 wt% of DMMP addition can increase the LOI value from 24.3% to 26.0%, where the commercial application standard of RPUF is achieved. Further benefits of using DMMP/MAPP system included restraining of total heat and smoke release, improvement of thermal stability, and char yield of RPUF. The thermogravimetric analysis (TGA)‐gas chromatography‐mass spectrometer (GC‐MS) results indicated that DMMP/MAPP could continuously release PO₂ and PO·free radicals in the gas phase. In addition, DMMP/MAPP exhibited the charring effect and barrier effect in the condensed phase, such bi‐flame retardant effect exerted by DMMP/MAPP resulted in the enhanced flame retardant property of RPUF.     

Fire retarded polyurethane foam composites based on steel slag/ammonium polyphosphate system: A novel strategy for utilization of metallurgical solid waste

A series of FR-RPUF composites were prepared by a one-step water foaming process with ammonium polyphosphate (APP) and steel slag (SS) as flame retardants. Thermogravimetric analysis (TG), limiting oxygen index (LOI), UL-94 vertical combustion test, microscale combustion calorimetry (MCC), TG-Fourier transform infrared spectrometry (TG-FTIR), scanning electron microscopy (SEM), Raman spectra and FTIR were used to investigate the thermal stability, flame retardancy, combustion performance, gas phase products, and char residue morphology of FR-RPUF composites. TG test results showed that the initial decomposition temperature (T_-5wt%) and char residue rate at 700°C of RPUF/APP/SS composites were significantly enhanced by the addition of APP and SS, and the thermal stability of the composites was improved. Flame retardant test results confirmed the significantly increased LOI values of RPUF/APP/SS composites with V-0 rating. TG-FTIR also confirmed the obviously decreased release of toxic gases and flammable gases in the combustion of RPUF/APP/SS composites. SEM and Raman spectra of char residues for the composites suggested that APP/SS system improved the compactness and graphitization degree of char layer for RPUF/APP/SS composite. The above researches provide a new strategy for the utilization of SS in fire safety engineering.     

Synergistic effect between phosphorus tailings and aluminum hypophosphite in flame‐retardant thermoplastic polyurethane composites

The massive accumulation of phosphorus tailings (PT) not only occupies land resources and also causes great threat to ecological environment and human security. It is of great significance to explore the resource utilization of PT in some fields. Herein, aluminum hypophosphite (AHP) and PT are blended together to enhance the flame retardancy of thermoplastic polyurethane (TPU) composites, and the synergistic effects between AHP and PT are investigated systematically. Cone calorimeter test (CCT) results indicate that the peak heat release rate (PHRR) and total heat release (THR) of the samples containing 25 wt% AHP are decreased by 89% and 68%, respectively, and the total smoke release (TSR) show a reduction of 58.8%, in comparison with those of neat TPU. For the sample TPU/22.5AHP/2.5PT, the PHRR, THR, and TSR are decreased by 91.2%, 70%, and 63%, respectively. Scanning electron microscopy (SEM) analysis results demonstrate that the addition of PT can facilitate the generation of dense and compact char layers, preventing the release of heat and smoke effectively. All the abovementioned results indicate that the synergistic effects are existed between AHP and PT for enhancing the fire safety of TPU composites, which can provide a new way for the utilization of PT.     

Joint‐aggregation intumescent flame‐retardant effect of ammonium polyphosphate and charring agent in polypropylene

In order to explore the structure mode of intumescent flame retardants (IFRs) with higher efficiency, IFR particles with joint‐aggregation structure (@IFR) were obtained through the treatment of ammonium polyphosphate (APP) and a charring agent (PT‐Cluster) in their aqueous solution. Then, the joint‐aggregation IFR effect was researched using its application in polypropylene. In case of 20 wt% IFR loading, the limiting oxygen index (LOI) value of @IFR/PP was 1.1% higher than that of 15APP/5PT‐Cluster/PP mixture, and a 1.6 mm‐thick @IFR/PP composite passed the UL 94 V‐2 rating test, while 15APP/5PT‐Cluster/PP demonstrated no flame‐retardant rating in UL 94 vertical burning tests. In a cone calorimeter test, @IFR also had a better inhibition effect on heat release. The average heat release rate (av‐HRR) value during 0 to 120 seconds of @IFR/PP was only 41 kW m^?2, which was 33.9% lower than that of the 15APP/5PT‐Cluster/PP. Furthermore, the peak heat release rate (pk‐HRR) of @IFR/PP was 20.5% lower than that of 15APP/5PT‐Cluster/PP, and the time to pk‐HRR of @IFR/PP was 710 seconds, while that of 15APP/5PT‐Cluster/PP was 580 seconds. The better inhibition effect on HRR and the delay of time to pk‐HRR were caused by the joint‐aggregated structure of @IFR, which can rapidly react to form stable and efficient char layers. This kind of join‐aggregation IFR effect has great significance in suppressing the spread of fire in reality. In addition, @IFR also increased the mechanical properties of PP composites slightly compared with the APP/PT‐Cluster mixture.     

Preparation and properties of an efficient smoke suppressant and flame‐retardant agent for thermoplastic polyurethane

APP@ETA, as a new type of flame retardant, was prepared by chemically modifying ammonium polyphosphate (APP) with ethanolamine (ETA) and applied to thermoplastic polyurethane (TPU) in this study. Then, the smoke suppression properties and flame‐retardant effects of APP@ETA in TPU composites were evaluated using smoke density test, cone calorimeter test, etc. And, the thermal degradation properties of flame‐retardant TPU composites were investigated by thermogravimetric analysis/infrared spectrometry. The smoke density test results indicated that APP@ETA could obviously improve the luminous flux of TPU composites in the test with or without flame. The cone calorimeter test results showed that total smoke release, smoke production rate and smoke factor of the composites with APP@ETA were significantly decreased than those of the composites with APP. For example, when the loading of APP@ETA or APP was 12.5 wt%, the total smoke release of the sample with APP@ETA decreased to 3.5 m²/m² from 6.0 m²/m², which was much lower than that of the sample with APP, reduced by 41.7%. The thermogravimetric analysis results demonstrated that APP@ETA could decrease the initial decomposition temperature and improve the thermal stability at high temperature for TPU composites. Copyright © 2017 John Wiley & Sons, Ltd.     

A flame‐retardant phosphate and cyclotriphosphazene‐containing epoxy resin: Synthesis and properties

A novel flame‐retardant epoxy resin, (4‐diethoxyphosphoryloxyphenoxy)(4‐glycidoxyphenoxy)cyclotriphosphazene (PPCTP), was prepared by the reaction of epichlorohydrin with (4‐diethoxyphosphoryloxyphenoxy)(4‐hydroxyphenoxy)cyclotriphosphazene and was characterized by Fourier transform infrared, ³¹P NMR, and ¹H NMR analyses. The epoxy resin was further cured with diamine curing agents, 4,4′‐diaminodiphenylmethane (DDM), 4,4′‐diaminodiphenylsulfone (DDS), dicyanodiamide (DICY), and 3,4′‐oxydianiline (ODA), to obtain the corresponding epoxy polymers. The curing reactions of the PPCTP resin with the diamines were studied by differential scanning calorimetry. The reactivities of the four curing agents toward PPCTP were in the following order: DDM > ODA > DICY > DDS. In addition, the thermal properties of the cured epoxy polymers were studied by thermogravimetric analysis, and the flame retardancies were estimated by measurement of the limiting oxygen index (LOI). Compared to a corresponding Epon 828‐based epoxy polymer, the PPCTP‐based epoxy polymers showed lower weight‐loss temperatures, higher char yields, and higher LOI values, indicating that the epoxy resin prepared could be useful as a flame retardant. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 972–981, 2000     

Crystallization kinetics and multiple melting phenomena of a flame‐retardant phosphorus containing copolyester

Melt, cold isothermal crystallization kinetics, and multiple melting phenomena are investigated by differential scanning calorimetry (DSC) for a flame‐retardant phosphorus containing copolyester. The crystallization kinetics was investigated by the Avrami equation. The Avrami exponent is about 2.6 for melt crystallization and about 2 for cold crystallization. The crystallization activation energy for melt crystallization and for cold crystallization is −64.7 and 145.5, respectively. Three melting endotherms are found in the DSC scan, and they are explained in terms of secondary crystallization, primary crystallization, and recrystallization during the scan. A strong evidence of a two‐stage crystallization mechanism was also observed in the DSC isothermal experiment and X‐ray diffraction. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2269–2277, 1999     

Lanthanum phenylphosphonate–based multilayered coating for reducing flammability and smoke production of flexible polyurethane foam

In the present work, lanthanum phenylphosphonate (LaPP)–based multilayered film was fabricated on the surface of flexible polyurethane (PU) foam by layer‐by‐layer self‐assembled method. The successful deposition of the coating was confirmed by scanning electron microscopy (SEM) and energy‐dispersive X‐ray (EDX). Subsequently, the thermal decomposition and burning behavior of untreated and treated PU foams were investigated by thermogravimetric analysis (TGA) and cone calorimeter, respectively. The TGA results indicated that T_max2 of treated PU foams were increased by approximately 15°C to 20°C as compared with untreated PU foam. The peak heat release rate (PHRR) and total heat release (THR) of PU‐6 (with 19.5 wt% weight gain) were 188 kW/m² and 20.3 MJ/m², with reductions of 70% and 15% as compared with those of untreated PU foam, respectively. Meanwhile, the smoke production of treated PU foam was suppressed after the construction of LaPP‐based coating.     

Microfluidic fabrication of polysiloxane/dimethyl methylphosphonate flame‐retardant microcapsule and its application in silicone foams

A novel and versatile route for fabricating flame‐retardant microcapsules via microfluidics technology is reported. The flame‐retardant microcapsules were prepared with a dimethyl methylphosphonate (DMMP) core and an ultraviolet‐curable (UV‐curable) polysiloxane shell. Furthermore, a UV‐curable polysiloxane was synthesized. The synthesis mechanism of UV‐curable polysiloxane and the curing mechanism of flame‐retardant microcapsules were analyzed. To verify that DMMP was encapsulated in the microcapsules, X‐ray fluorescence was used before and after microencapsulation. The resulting microcapsules were well monodispersed and exhibited a good spherical shape with a smooth surface. In addition, the size of the microcapsules decreased dramatically with an increasing flow‐rate ratio of the middle‐/inner‐phase or outer‐phase flow rate. The thermal stability of the microcapsules was worse than shell materials but superior to DMMP. Silicone foams (SiFs) with microcapsules prepared using a dehydrogenation method achieved a relatively higher limiting oxygen‐index value than the pure SiF, which indicated that the microcapsules could enhance the flame retardation of SiFs effectively. Because of the polysiloxane shell, the microcapsules had good compatibility with SiFs, and the influence of microcapsules on the mechanical properties of SiFs was unremarkable.     

Sound absorption behavior of flexible polyurethane foams including high molecular‐weight copolymer polyol

Noise pollution is an important issue for automotive industries. In this article, the high molecular‐weight copolymer polyol is blended in the polyol mixtures for fabricating flexible polyurethane foams to improve sound absorption efficiency. Changes of cavity size and material density of the foams are negligible by inclusion of copolymer polyol in the polyol mixture, but the closed pore ratio and specific airflow resistance increase for the copolymer polyol content higher than 20 wt% because of changes of phase separation behavior from drainage flow rate reduction that occurs with increased viscosity. Sound absorption efficiency increases with increasing copolymer polyol content up to 20 wt%, but it decreases beyond this point. The sound absorption property mainly results from the closed pore ratio, not from the cavity size. The compression strength increases with increasing copolymer polyol contents by increased amount of hard segments. Therefore, an optimum amount of high molecular‐weight polyol is recommended for enhanced sound absorption property.     

A liquid phosphorous flame retardant combined with expandable graphite or melamine in flexible polyurethane foam

A systematic series of flexible polyurethane foams (FPUF) with different concentrations of flame retardants, bis([dimethoxyphosphoryl]methyl) phenyl phosphate (BDMPP), and melamine (MA) or expandable graphite (EG) was prepared. The mechanical properties of the FPUFs were evaluated by a universal testing machine. The pyrolysis behaviors and the evolved gas analysis were done by thermogravimetric analysis (TGA) and TGA coupled with Fourier-transform infrared (TG-FTIR), respectively. The fire behaviors were studied by limiting oxygen index (LOI), UL 94 test for horizontal burning of cellular materials (UL 94 HBF), and cone calorimeter measurement. Scanning electronic microscopy (SEM) was used to examine the cellular structure's morphology and the postfire char residue of the FPUFs. LOI and UL 94 HBF tests of all the flame retarded samples show improved flame retardancy. BDMPP plays an essential role in the gas phase because it significantly reduces the effective heat of combustion (EHC). This study highlights the synergistic effect caused by the combination of BDMPP and EG. The measured char yield from TGA is greater than the sum of individual effects. No dripping phenomenon occurs during burning for FPUF-BDMPP-EGs, as demonstrated by the result of the UL 94 HBF test. EG performs excellently on smoke suppression during burning, as evident in the result of the cone calorimeter test. MA reduces the peak heat release rate (pHRR) significantly. The synergistic effect of the combination of BDMPP and EG as well as MA offers an approach to enhance flame retardancy and smoke suppression.     

Effects of metal oxides on intumescent flame‐retardant polypropylene

Variable amounts of transition metal oxides (MO), such as MnO₂, ZnO, Ni₂O₃, etc., were incorporated into blends of polypropylene (PP)/ammonium polyphosphate (APP)/dipentaerythritol (DPER) with the aim of studying and comparing their effects with main‐group MO on intumescent flame retardance (IFR). The PP/IFR/MO composites were prepared using a twin‐screw extruder, and the IFR behavior was evaluated through oxygen index and vertical burning tests. The progressive enhancement of flame retardancy has proved to be strongly associated with the interaction between APP and MO. With the aid of thermogravimetry (TG) analysis, Fourier transform infrared (FTIR) spectra and scanning electron microscopy, Ni₂O₃ has been shown to be the most effective among the aforementioned three MO. The flame‐retardant mechanism of the IFR system is also discussed in terms of catalytic charring, which relates to complex formation through the d‐orbitals of the transition metal elements. It is considered that the melt viscosity of a PP/APP/DPER blend containing Ni₂O₃ corresponds well to the gas release with increasing temperature. Copyright © 2009 John Wiley & Sons, Ltd.     

Mechanical and flame‐retardant properties of biodegradable polylactide composites with hyperbranched silicon‐containing polymer

A hyperbranched polymer (HBP‐B2) containing siloxane chains was synthesized via bulk polymerization of diepoxide with a primary amine in the presence of monoepoxide. The weight‐average molecular weight of the prepared polymers was approximately 9200. Composites of polylactide (PLA) with aluminum trihydroxide (ATH) and the HBP‐B2 were prepared via direct melt compounding using a brabender. The test results showed that the LOI could be raised to 34% for the PLA composite with 25 wt% ATH and 5% HBP‐B2. The surface thermal profile of the composite during UL94 V test was further captured by an infrared camera, which was helpful to understand the flame‐retardant properties of the different samples. A V‐0 rating could be achieved by adding ATH and HBP‐B2 to the PLA matrix. Incorporation of HBP‐B2 as a plasticizer could increase the impact strength of a PLA blend or composite. For example, an addition of 10 wt% of HBP and 20 wt% ATH increased the elongation at break from 5% for neat PLA to 155% for the PLA composite.     

Effects of biopitch on the properties of flexible polyurethane foams

Biopitches are industrial residues obtained by the distillation of the tar recovered during Eucalyptus charcoal production and can be used as a renewable polyol source. Flexible polyurethane foams were prepared with different proportions of biopitch and HTPB (hydroxyl-terminated polybutadiene) and using polymeric MDI (4,4′ diphenyl methane diisocyanate), N,N dimethylcyclohexylamine as a catalyst and water as a blowing agent. Elemental analysis, thermal analysis (TG/DSC), Fourier Transform Infrared Spectroscopy (FTIR), scanning electronic microscopy (SEM), and density results were used aiming to discuss the contribution of biopitch to foams properties. The higher the biopitch content, the higher the thermal stability and the lower the density of the flexible foams (air atmosphere), behaviors similar to those of lignin-based polyurethanes. Biopitch enhanced the oxygen content of the polyurethane foams synthesized, and their reaction with HTPB resulted in stable foams.     

The synergistic flame‐retardant effect of O‐MMT on the intumescent flame‐retardant PP/CA/APP systems

The flame retardancy of a novel intumescent flame‐retardant polypropylene (IFR‐PP) system, which was composed of a charring agent (CA), ammonium polyphosphate (APP), and polypropylene (PP), could be enhanced significantly by adding a small amount (1.0 wt%) of an organic montmorillonite (O‐MMT). The synergistic flame‐retardant effect was studied systematically. The thermal stability and combustion behavior of the flame‐retarded PP were also investigated by thermogravimetric analysis (TGA), limiting oxygen index (LOI), vertical burning test (UL‐94), scanning electronic microscopy (SEM), and cone calorimeter test (CCT). TGA results demonstrated that the onset decomposition temperatures of IFR‐PP samples, with or without O‐MMT, were higher than that of neat PP. Compared with IFR‐PP, the LOI value of IFR‐PP containing 1.0 wt% O‐MMT was increased from 30.8 to 33.0, and the UL‐94 rating was also enhanced to V‐0 from V‐1 when the total loading of flame retardant was the same. The cone calorimeter results showed that the IFR‐PP with 1.0 wt% of O‐MMT had the lowest heat release rate (HRR), total heat release (THR), total smoke production (TSP), CO production (COP), CO₂ production (CO₂P), and mass loss (ML) of all the studied IFR‐PP samples, with or without O‐MMT. All these results indicated that O‐MMT had a significantly synergistic effect on the flame‐retardancy of IFR‐PP at a low content of O‐MMT. Copyright © 2009 John Wiley & Sons, Ltd.     

Durable flame‐retardant finishing for polyamide 66 fabrics by surface hydroxymethylation and crosslinking

This paper describes an attempt to develop a durable finishing method in order to improve the fire performance of polyamide 66 fabrics. Hydroxymethylation with a 36% formaldehyde aqueous solution in association with a pad‐curing process to enable the fabric to react with flame‐retardant solutions was used in the finishing process. The fire performance of treated samples was characterized by limiting oxygen index (LOI) and vertical flammability tests, and the results show that the LOI value can increase from 21.6% to 46.2%. The thermal behavior of untreated and treated polyamide 66 fabrics was investigated by using thermogravimetic analysis and differential scanning calorimetry. Furthermore, residual char of treated fabric sample is much higher than that of untreated fabric sample. Fourier transform infrared spectroscopy proves that the substituted hydroxymethyl groups do exist on the molecular chain of polyamide fabric sample after surface modification. The morphology of residue char of polyamide 66 fabric samples was analyzed by scanning electron microscope, and the mechanical properties were also investigated and discussed. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis of a novel DPPA‐containing benzoxazine to flame‐retard epoxy resin with maintained thermal properties

The flame‐retarded epoxy resin with improved thermal properties based on environmentally friendly flame retardants is vital for industrial application. Hereby, a novel reactive‐type halogen‐free flame retardant, 10‐(3‐(4‐hydroxy phenyl)‐3,4‐dihydro‐2H‐benzo[e] [1,3] oxazin‐4‐yl)‐5H‐phenophosphazinine 10‐oxide (DHA‐B) was synthesized via a two‐step reaction route. Its structure was characterized using ¹H, ¹³C, and ³¹P NMR and HRMS spectra. For 4,4′‐diaminodipheny ethane (DDM) and diglycidyl ether of bisphenol A (DGEBA)‐cured systems, the epoxy resin with only 2 wt% loading of DHA‐B passed V‐0 rating of UL‐94 test. Significantly, its glass transition temperature (T_g) and initial decomposition temperature (T_5%) were as high as 169.6°C and 359.6°C, respectively, which were even higher than those of the corresponding original epoxy resin. Besides, DHA‐B decreased the combustion intensity during combustion. The analysis of residues after combustion suggested that DHA‐B played an important role in the condensed phase.     

高活性阻燃聚醚多元醇的合成

五溴苯基缩水甘油醚;阻燃PU泡沫;高活性阻燃聚醚多元醇的合成