Reactive,intumescent, halogen‐free flame retardant for polypropylene

A reactive, intumescent, halogen‐free flame retardant, 2‐({9‐[(4,6‐diamino‐1,3,5‐triazin‐2‐yl)amino]‐3,9‐dioxido‐2,4,8,10‐tetraoxa‐3,9‐diphosphaspiro[5.5]undecan‐3‐yl}oxy)ethyl methacrylate (EADP), was synthesized through a simple three‐step reaction from phosphorus oxychloride, pentaerythritol, hydroxyethyl methacrylate, and melamine. EADP exhibited excellent thermal stability and char‐forming ability, as revealed by thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The TGA results show that the temperature at 5% weight loss was 297.8°C and the char yield at 700°C was 51.75%. SEM observation revealed that the char showed a continuous and compact surface and a cellular inner structure with different sizes. Composite of polypropylene (PP) with a 25 wt % addition of EADP (PP/EADP25) passed the UL‐94 V‐0 rating and showed a limiting oxygen index value of 31.5. Compared with those of neat PP, the flexural strength and modulus values of PP/EADP25 were somewhat improved, the tensile strength was basically unchanged, and the notched Izod impact strength was slightly decreased. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40054.     

Tensile and flammability properties of polypropylene‐based RTPO/clay nanocomposites for cable insulating material

Nanocomposites of polypropylene‐based RTPO with organically modified clays were prepared by melt compounding of three components, that is, polypropylene‐based RTPO, maleic anhydride‐grafted polypropylene oligomer (PPgMA), and organically modified clay. Their morphologies, tensile behaviors, and flammability properties were investigated. In the clay nanocomposites, the silicate layers were dispersed at the nanometer level, which was confirmed by X‐ray diffraction and transmission electron microscopy. The tensile yield strength of nanocomposites containing 10 wt % clay exhibited 2.8 times higher value compared with that of neat resin. The combustion behavior of the nanocomposites was evaluated by measuring the heat release rate (HRR) using cone calorimetry. The peak HRR was lowered greatly and the char yield was very high compared with those of neat resin. However, these flame retardant properties of clay are not sufficient as a flame retardant used alone in cable applications. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2375–2381, 2005     

The flame retardancy and mechanical properties of jute/polypropylene composites enhanced by ammonium polyphosphate/polypropylene powder

Surface flame retarded jute/polypropylene composites (J/P/A) were prepared via a modified strategy: the mixture of PP and APP powder was spread over the surface of jute/PP nonwoven felts, and then transformed into the flame retarded layer by the hot pressing process. The flame retardancy and thermal properties of composites were analyzed by limit oxygen index (LOI), horizontal burning rate (HBR), thermogravimetric analyses (TGA), and differential scanning calorimetry (DSC). We demonstrated that the flame retardancy and mechanical properties of composites was significantly improved compared with those obtained by presoaking the nonwoven fiber felts in flame retardant (FR) solvent before hot pressing. The mechanism of thermal degradation of jute fiber and flame‐retardant mechanism of composites were analyzed by Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR), and scanning electron microscope (SEM). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43889.     

氢氧化镁阻燃剂的表面改性及其在聚丙烯中的应用

采用不同改性剂对氢氧化镁进行表面改性处理，通过实验发现采用4％的硬脂酸钠处理后的氢氧化镁阻燃剂在聚丙烯体系中分散均匀，当氢氧化镁在聚丙烯体系中的添加量达65％时，达到了理想的阻燃效果。     

Mechanical properties of flame retardant filled polypropylene composites

The flammability performance and mechanical behaviors for halogen‐based and non‐halogen‐based flame retardant (FR) filled polypropylene (PP) composites were investigated in this study. The halogen‐based FR system consisted of a mixture of brominated phosphate ester and antimony trioxide (BR), and the halogen‐free FR was a magnesium hydroxide (MH). It was found from limiting oxygen index measurements that 60 wt % of MH was needed in order to achieve the same degree of flammability as the composite containing only 30 wt % of BR. Scanning electron microscopy examinations of the fractured specimens indicated that the interfacial bond strength between PP and MH was stronger than that for PP and BR. The notched Charpy impact strength and the impact fracture toughness were measured and compared. The discrepancies between the two impact test results could be correlated after kinetic energy correction was applied to the Charpy impact strengths. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2718–2728, 2001     

Influence of gamma radiation on compatibilized LLDPE/magnesium hydroxide/sepiolite composites

The influence of gamma irradiation on the properties of compatibilized linear low‐density polyethylene/magnesium hydroxide (MH)/sepiolite composites has been investigated. Vinyl triethoxy silane and maleated polyethylene have been used as compatibilizers. The compatibilizing effect in the composites is confirmed by the Fourier transform infrared spectra, which showed the presence of additional chemical bonds, which are responsible for the enhanced polymer‐filler interaction. As a result, the miscibility of the polar additives into the nonpolar polymer matrix is enhanced. The scanning electron micrographs revealed that the additives are well embedded and uniformly dispersed in the polymer matrix without any voids. The known thermal decomposition temperature of MH (～ 350°C) is also increased in the compatibilized composites. In addition, 150 kGy irradiated composite showed a remarkable improvement of 37°C in the onset degradation temperature of unirradiated composite. Furthermore, the formation of radiation crosslinked structure in the composites also improved the mechanical properties of the composites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of particle size and content of magnesium hydroxide on flame retardant properties of asphalt

The flame‐retardant properties of asphalt for some building applications are very important. This article is mainly focused on the influence of particle size and content of magnesium hydroxide (MH) on the flame‐retardant properties of asphalt. The limit oxygen index and cone calorimeter results indicate that as the MH content and mesh number increase, the flame‐retardant properties of MH‐filled flame‐retardant asphalt show a rising trend. But the role of particle size in smoke suppression is not obvious. Several tests confirm that the dispersion of the MH have some influence on the flame‐retarding effect of asphalt. The 3000 mesh MH for the preparation of flame‐retardant asphalt shows optimal performance. The experimental data show that the softening point of flame‐retardant asphalt increases, but the ductility and penetration decrease with increasing MH content. MH affects the asphalt viscosity, but not affects the adhesion of the asphalt to gravel. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical performance and flame retardancy of polypropylene composites containing zeolite and multiwalled carbon nanotubes

Intumescent‐flame‐retarded polypropylene (PP‐IFR) composites were prepared by the incorporation of methyl hydrogen siloxane treated ammonium polyphosphate and dipentaerythritol in a twin‐screw extruder. The effects of zeolite (Z), multiwalled carbon nanotubes (CNTs), and maleic anhydride grafted polypropylene on the flame retardancy, mechanical properties, and thermal stability of PP‐IFR were investigated. The addition of Z and CNT promoted the flame retardancy of PP‐IFR, and the highest limited oxygen index was 35.6%, obtained on PP‐M‐IFR‐2–Z, for which the heat‐release rate, total heat release, and smoke production rate based on cone calorimetry analyses decreased by 45.0, 51.0, and 66.3%, respectively, in comparison with those values of the PP‐IFR composites. Additionally, scanning electron microscopy analyses showed that there was a good interface interaction between the polypropylene matrix and additives. The flexural, tensile, and impact strengths of the PP‐IFR composites were improved significantly with the incorporation of CNT. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42875.     

Construction of thermoplastic cellulose esters matrix composites with enhanced flame retardancy and mechanical properties by embedding hydrophobic magnesium hydroxide

Biomass-based composites with renewability and biodegradability have attracted extensive researches, but their applications are hindered by poor mechanical properties and flame retardancy. Cellulose ester matrix composites (CEMC), a kind of biomass-based composites, were prepared with inorganic crystals as flame retardant and reinforcement. Cellulose acetate oleate (CAO) prepared by mechanical activation-assisted solid-phase reaction was used as thermoplastic matrix. Hydrophobic oleate-magnesium hydroxide (O-MH), which was surface-modified with oleic acid, was embedded into CAO to prepare O-MH/CAO composites by hot pressing. The introduction of oleoyl contributed to favorable thermoplasticity of cellulose ester, resulting in enhanced thermal stability and mechanical properties of CEMC. The uniform dispersion of O-MH in the CAO matrix via metal–organic coordination increased the mechanical properties and flame retardancy of O-MH/CAO composites, ascribing to the toughening effect and combustion inhibition effect induced by O-MH. This study provides a feasible technology for fabricating the CEMC with outstanding thermal stability and mechanical properties.     

PP成炭阻燃研究进展

从聚合物成炭、含硅化合物协效成炭、金属及其化合物催化成炭和无机纳米材料协效成炭等方面,综述了聚丙烯(PP)在成炭阻燃领域的研究进展。通过添加不同的协效成炭剂可以提高PP燃烧时的成炭量和成炭效率。运用多种方法协同作用正成为PP阻燃的研究方向。     

Component ratio effects of hyperbranched triazine compound and ammonium polyphosphate in flame‐retardant polypropylene composites

A hyperbranched derivative of triazine group (EA) was synthesized by elimination reaction between ethylenediamine and cyanuric chloride. The different‐mass‐ratio EA and ammonium polyphosphate (APP) were mixed and blended with polypropylene (PP) in a constant amount (25%) to prepare a series of EA/APP/PP composites. The component ratio effect of EA/APP on the flame‐retardant property of the EA/APP/PP composites was investigated using the limiting oxygen index (LOI), vertical burning (UL‐94), and cone calorimetry tests. Results indicated that the EA/APP/PP (7.50/17.50/75.00) composite with the appropriate EA/APP mass ratio had the highest LOI, UL94 V‐0 rating, lowest heat release rate, and highest residue yield. These results implied that the appropriate EA/APP mass ratio formed a better intumescent flame‐retardant system and adequately exerted their synergistic effects. Furthermore, average effective combustion heat values revealed that EA/APP flame retardant possessed the gaseous‐phase flame‐retardant effect on PP. Residues of the EA/APP/PP composites were also investigated by scanning electron microscopy, Fourier‐transform infrared, and X‐ray photoelectron spectroscopy. Results demonstrated that the appropriate EA/APP mass ratio can fully interact and lock more chemical constituents containing carbon and nitrogen in the residue, thereby resulting in the formation of a dense, compact, and intumescent char layer. This char layer exerted a condensed‐phase flame‐retardant effect on EA/APP/PP composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41006.     

Flame resistant properties of LDPE/PLA blends containing halogen-free flame retardant

In this study, mixing petroleum-based low-density polyethylene (LDPE) with biodegradable poly(lactic acid) (PLA) is used as polymer matrix. Boron compounds, metal hydroxides, melamine (MLM), ammonium polyphosphate (APP), and pentaerythritol (PER) were used as reinforcement materials to improve flame resistance of polymer matrix. The composite materials were characterized by Fourier transform infrared spectroscopy, limiting oxygen index (LOI), thermogravimetric analysis, mechanical test, and scanning electron microscopy analyses. The LOI analysis showed that for samples, which included MLM, APP, and PER, the LOI values were dramatically improved. Especially, the LOI value of sample Q (LDPE80/PLA20/APP30/PER15/MLM15/ZB3) was enhanced about 95.17% compared to polymer mixing. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48960.     

聚烯烃弹性体/聚丙烯热塑性弹性体的制备及力学性能

以过氧化物为硫化剂,用动态硫化法制备了聚烯烃弹性体(POE)/聚丙烯(PP)热塑性弹性体,研究了硫化剂用量、填料种类和加工次数对体系力学性能的影响。结果表明,增加硫化剂用量可以提高体系的拉伸强度,降低拉伸永久变形和压缩永久变形。碳酸钙和滑石粉对POE/PP体系无明显增强作用,炭黑的增强作用较此二者明显一些,这三种填料加入后都会使体系的扯断伸长率降低而硬度增大。加入石蜡油会使体系的扯断伸长率和压缩永久变形增大、硬度和拉伸强度降低。加工次数对POE/PP体系的力学性能无明显影响,说明体系具有较好的重复加工性能。     

Synthesis of a novel azaphosphorine flame retardant and its application in epoxy resins

A novel P? C? N bond containing azaphosphorine, 5‐(4‐hydroxy)anilinomethyl‐1,3‐di(4‐hydroxy)phenyl‐1,3,5‐diazaphosphorinane (ADDPP‐OH), which could be used as both a cocuring agent and a flame‐retarding agent for epoxy resins (EPs), was synthesized from tetrakis(hydroxymethyl)phosphonium sulfate and characterized by FTIR, ¹H‐NMR, ¹³C‐NMR, ³¹P‐NMR, and so on. Compared with the pure EP, the ADDPP‐OH–EP composites showed increased decomposition temperatures and char yields. When the content of ADDPP‐OH was 10 wt %, the cured EP composite possessed a limiting oxygen index value of 33.7% and passed the V‐0 rating of the UL‐94 test. The mechanical properties of the ADDPP‐OH–EP composites was improved because of the increased crosslinking density. In addition, the morphology of the residual char indicated an intumescent and multiporous structure in the inner space and a compact and continual appearance in the outer layer; this was important in preventing the materials from burning further. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45721.     

Effect of charring agent THEIC on flame retardant properties of polypropylene

Tris(2‐hydroxyethyl) isocyanurate (THEIC) was used as charring agent and combined with ammonium polyphosphate (APP) to form an intumescent flame retardant (IFR) for polypropylene (PP). The flame retardancy and combustion performance of PP/IFR composite was tested by limiting oxygen index (LOI), UL‐94 vertical burning test and cone calorimeter. The results showed that PP/IFR composite had highest LOI of 34.8 and obtained V‐0 rating when 30 wt % IFR was loaded and mass ratio APP/THEIC was 2 : 1. The peak heat release (PHRR) and total heat release (THR) values of PP composite containing FRs were remarkably reduced compared with that of pure PP. However, water resistant test demonstrated the PP/IFR composite had poor flame retardant durability, both the LOI value and UL‐94 V‐rating decreased when PP/IFR composite was soaked in water at 70°C after 36 h. The degradation process and the char morphology of IFR and PP/IFR composite were investigated by TGA and SEM images. The possible reaction path between APP and THEIC in the swollen process was proposed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41214.     

Property of intrinsic flame retardant epoxy resin cured by functional magnesium organic composite salt and diethylenetriamine

An efficient intrinsic flame retardants composite was prepared by curing epoxy resin with a functional magnesium organic composite salt (FMOCS, 0.685 ± 0.3 nm) and diethylenetriamine (DETA). Curing behavior, thermal and flame‐retardant properties of the cured epoxy resins were systematically investigated by infrared spectrum (FTIR), thermogravimetric analysis (TGA), vertical burning test (UL‐94) and limited oxygen index (LOI) measurement. It was found that flame retardancy and mechanical properties of the cured composite are significantly enhanced compared with DETA/EP. The LOI of the EP reached to 33%, which is much higher than the DETA/EP (19%) or its IFR composite (31%) in the optimal addition of ammonium polyphosphate (APP, 18.69 wt %), pentaerythritol (PER, 6.21 wt %) and FMOCS (3.50 wt %). Furthermore, the mechanical properties of the composite material measurement results to imply that it can enhance tensile strength (150%) and bending strength (88%) rather than DETA/EP, which were tested by impact testing machine and microcomputer control electron universal testing machines. Copyright © 2016 John Wiley & Sons, Ltd.     

Structure and properties of polypropylene composites filled with magnesium hydroxide

Silane and silicone oil modified superfine magnesium hydroxide (MH) was filled into polypropylene (PP) as a flame retardant. The PP and flame‐retarded PP composites were studied for their mechanical properties and rheological behaviors by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), limiting oxygen index (LOI), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The results showed that the addition of MH improved flame retardancy of PP/MH composites, but seriously deteriorated mechanical properties of the composites. Surface treatment of MH could significantly improve tensile and impact strength of PP/MH composite because of its enhanced interfacial adhesion between MH and PP matrix. DSC results showed that MH had heterogeneous nucleation effect on PP. Surface treatment of MH weakened its heterogeneous nucleation effect. POM results showed that the dispersion of MH particles played an important role in the crystalline morphology and spherulite size of PP crystals. TGA indicated that MH greatly enhanced the thermal stability of PP. The introduction of treatment agent further improved the thermal oxidative stability of the composite. According to LOI, silane‐treated MH greatly enhanced flame retardancy of PP/MH composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4943–4951, 2006     

Preparation and properties of modified aluminum diethylphosphinate flame retardant for low-density polyethylene

To improve the flame retardancy of low-density polyethylene (LDPE) and mechanical properties of LDPE composites, phenol-formaldehyde aluminum diethylphosphinate microcapsules (PF@ADP) was prepared by in-situ polymerization with phenol-formaldehyde (PF) resin as the wall material and halogen-free flame-retardant aluminum diethylphosphinate (ADP) as the core material. The effects of PF@ADP on flame retardancy and mechanical properties of LDPE were investigated by methods of combustion experiments, mechanical analysis, thermogravimetric analysis (TGA), and smoke density analysis. The results indicated that, compared with ADP/LDPE composites, the flame retardancy and mechanical properties of PF@ADP/LDPE were obviously improved. With the addition of 20 wt% PF@ADP (PF:ADP = 3:7), the limit oxygen index (LOI) of LDPE composites increased to 30.7% and UL-94 reached V-1 grade. The tensile strength and elongation at break reached 12.5 MPa and 431.2%, which was 20.2% and 23.1% higher than that of ADP/LDPE with the same addition. The addition of PF@ADP was beneficial to the smoke suppression of LDPE.     

Synthesis of FePP@MoS2@Ni-MOF composites for improving thermal and flame retardant safety properties of polyurea

Polyurea (PUA) is widely used as a coating in construction, tunnels, bridges, and other fields because of its excellent performance. However, its combustion emits toxic gases and smoke, hindering escape and posing potential fatality risks. Enhancing the flame retardancy of PUA is crucial for safety and expanding its applications. The synthesis of two-dimensional FePP nanosheets was reported in this paper, employing the solvothermal method, followed by the sequential growth of MoS₂ and Ni-MOF to establish a multilayer composite structure. The elemental composition and morphology of the synthesized FePP@MoS₂@Ni-MOF flame retardants were characterized and analyzed. The flame retardant properties of polyurea composites with varying amounts of FePP@MoS₂@Ni-MOF were investigated using Cone calorimeter tests. The results showed that the prepared flame retardant had good thermal stability and significantly improved fire safety properties. The PUA/FePP@MoS₂@Ni-MOF 3.0 composite exhibited notable improvements compared to pure PUA. Specifically, the peak heat release rate, total heat release rate and peak smoke production rate were reduced by 39.76%, 29.33% and 17.86%, respectively, while total smoke production and total CO production (COP) were reduced by 21.30% and 54.47%. This study provides new insights and experimental basis for the technological development of novel flame retardant coating materials.     

The mechanical properties and thermal performances of polypropylene with a novel intumescent flame retardant

A novel intumescent flame retardant: tetra‐spirophosphoryl‐benzoguanamine (TSPB) containing three constituents was used as a new flame retardant for polypropylene to prepare flame‐retardant materials, whose flammability and thermal behavior were studied by the limited oxygen index (LOI), thermogravimetric analysis (TGA), in addition whose mechanical properties were investigated in this work. It was found that when the addition of TSPB was 25 wt %, the LOI value of the PP could achieve to 29.5 and pass the UL‐94 V‐0 rating test. The TGA data showed that TSPB could enhance the thermal stability of PP and effectively increase the char residue formation. The mechanical performance test showed that the addition of TSPB improve the mechanical performances of PP to some extent. Thus, the trinity intumescent flame retardant TSPB is good to modify PP. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010