Effect of intumescent compositions on flammable properties of ethylene vinyl acetate and polypropylene

An intumescent flame retardant (IFR) system was prepared by 2 ways. Firstly, bis(2,6,7‐trioxa‐1‐phosphabicyclo[2,2,2]octane‐1‐oxa‐4‐hydroxymethyl) phosphonate methyl (bis‐PM) was synthesized and characterized by ¹H nuclear magnetic resonance (NMR), ³¹P NMR, and Fourier transform infrared spectroscopies. This carbonization agent was mixed with melamine (ME), ammonium polyphosphate (APP), and pentaerythritol (PER) to constitute an IFR system. Secondly, an IFR system by reaction was prepared by reaction, and the presence of compositions in product was confirmed by ¹H NMR and Fourier transform infrared. Both of systems enhanced the flammable retardation of ethylene vinyl acetate (EVA) and polypropylene (PP). Flammability and thermal behaviors of IFR‐EVA and IFR‐PP were investigated by vertical burning test (UL‐94 V) and thermogravimetric analysis. Results indicated that the IFR systems performed excellent flame retardancy and antidripping ability for PP. At 30 wt% loading, the optimum flame retardant formulations that are bis‐PM/ME: 4/1, bis‐PM/ME/PER: 3/1/1, APP/ME/PER: 3/1/1, and bis‐PM/ME/PER/APP: 1.5/1.5/1/1 give UL‐94 V‐0 rating. However, V‐0 rating results were only obtained for EVA when systems contain bis‐PM/ME: 4/1 and bis‐PM/ME/PER: 3/1/1. The char yield from decomposition of the IFR‐EVA and IFR‐PP has effects on the flame retardancy and antidripping behaviors of EVA and PP.     

Thermal and flame retardant properties of ethylene‐vinyl acetate copolymer/modified multiwalled carbon nanotube composites

The synthesized flame retardant 9,10‐dihydro‐9‐oxa‐10‐phosphaphanthrene‐10‐oxide/vinyl methyl dimethoxysilane (DV) was used to modify multiwalled carbon nanotubes (MWNTs). The results of FTIR, ¹H‐NMR, and TGA measurements show that DV has been covalently grafted onto the surfaces of MWNTs, and the MWNTs‐g‐DV is obtained successfully. Transmission electron microscopy images show that a core‐shell nanostructure appears with MWNTs as the core and the DV thin layers as the shell, and the modified MWNTs with DV can achieve better dispersion than unmodified MWNTs in EVM matrix. Thermogravimetric analysis and cone calorimeter tests indicate that the thermal stability and flame retardant are improved for the presence of the MWNTs in EVM matrix. Moreover, the improvement is more evident for EVM/MWNTs‐g‐DV composite compared to unmodified MWNTs‐based composite, which can be attributed to the better dispersion of the DV‐modified MWNTs and to the chemical structure of the combustion residue. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Study on the flame retardancy of EVM/magnesium hydroxide composites optimized with a flame retardant containing phosphorus and silicon

A novel phosphorus‐silicon‐containing flame retardant, spirocyclic pentaerythritol bisphosphorate disphosphoryl chloride/9, 10‐dihydro‐9‐oxa‐10‐phosphaphanthrene‐10‐oxide/vinyl methyl dimethoxysilane (SPDV), was synthesized successfully and used for optimizing the flame retardancy of ethylene‐vinyl acetate copolymer (EVM) rubber/magnesium hydroxide (MDH) composites. The microstructure of SPDV was characterized and determined by Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy. Thermogravimetric analysis (TGA) showed that SPDV had good charring effect in air even at high temperature (800°C). The flame retardancy of the optimized EVM/MDH composites by SPDV was investigated by limiting oxygen index (LOI), cone calorimeter, and UL‐94 vertical burning tests. A higher LOI value (29.4%) and better UL‐94 rating (V‐0) can be achieved for the optimized EVM/MDH composite (EVM‐7) than EVM/MDH composite without SPDV (EVM‐3) with the total loading of additives. The HRR decreased and residual mass increased gradually as the loading of SPDV increased for the optimized EVM/MDH composites. There existed distinct synergistic intumescent flame‐retardant effect between SPDV and MDH in EVM matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A novel phytic acid based flame retardant to improve flame retardancy,hydrophobicity and mechanical properties of linear low-density polyethylene

Exploiting high phosphorus content of phytic acid, it was grafted onto magnesium hydroxide (MH) by neutralization reaction to obtain MGPA, a flame retardant. A current study investigated the effect of MGPA on hydrophobicity, flame retardancy, and mechanical properties of MGPA-linear low-density polyethylene (LLDPE) composites. The LLDPE composite with 50 parts of MGPA has the better flame retardancy and thermal stability with a limiting oxygen index of 23.3%, which is higher than that of neat LLDPE (17%). In addition, MGPA could effectively promoted LLDPE to form a continuous and compact char residue during combustion, which reduce the peak of heat release rate and total smoke production value of LLDPE composite by 70% and 36%, respectively, and the char residue rate increase to 67.5%. Furthermore, the maximum of loss-rate showed by LLDPE composite with MGPA reduce to 1.25%/min while the value of LLDPE composite with MH is 1.8%/min. Meanwhile, the LLDPE composite with MGPA show remarkable elongation at break and hydrophobicity, which are 398% and 99°, respectively. In addition, this study presents a substantial flame retardancy and interfacial compatibility of MGPA for extending the applications of flame-retardant LLDPE composites.     

Stearic acid surface modifying Mg(OH)2: Mechanism and its effect on properties of ethylene vinyl acetate/Mg(OH)2 composites

In this article, FTIR spectra and ESEM images were employed to evaluate the effect of stearic acid surface modification of Mg(OH)₂. As a result, the absorbing peak intensity of organic group on Mg(OH)₂ increased with the coating amount of stearic acid increasing and there was no so‐called surface saturation as expected. The results indicated stearic acid surface treatment of Mg(OH)₂ belonged to the acid–base reaction between stearic acid and Mg(OH)₂, and it would not stop until Mg(OH)₂ was reacted completely. In addition, stearic acid surface treatment of Mg(OH)₂ had remarkable influence on the properties of ethylene vinyl acetate/Mg(OH)₂ composites. With the increasing coating amount of stearic acid, the composites had decreased tensile strength, increased elongation at break, and deteriorated flame retardancy, compared with the composites filled with the uncoated Mg(OH)₂. However, stearic acid surface treatment of Mg(OH)₂ benefited processing ability of composites, and the composites had better processing ability as the coating amount of stearic acid increased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synergistic effect of MXene on the flame retardancy and thermal degradation of intumescent flame retardant biodegradable poly (lactic acid) composites

The effect of Ti₃C₂ MXene nanosheets on the intumescent flame retardant (IFR) poly (lactic acid) (PLA) composites was investigated among a series of PLA/IFR/MXene, which were prepared by melt blending 0-2.0 wt% MXene, 10.0 wt%-12.0 wt% IFR and PLA together. The results of limiting oxygen index (LOI) and vertical burning (UL-94) discover that the combination of 0.5 wt% MXene and 11.5 wt% IFR synergistically improves the fire safety of PLA to reach UL-94 V-0 rating with LOI value of 33.0%. The PLA/IFR/MXene composites perform an obvious reduction in peak of heat release rate (HRR) in cone calorimeter tests (CCTs). Furthermore, the carbon residues after CCTs were characterized by scanning electron microscope (SEM), laser Raman spectroscopy (LRS), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). It is demonstrated that both the titanium composition of the MXene structure and the characteristics of the two-dimensional material enhance the PLA/IFR/ MXene composite materials' ability to produce a dense barrier layer to resist burnout during thermal degradation.     

Flame retardancy and thermal stability of ethylene-vinyl acetate copolymer nanocomposites with alumina trihydrate and montmorillonite

The development of fire retardant for wire and cable sheathing materials has oriented toward low smoke and halogen-free flame retardant technology to achieve better safety for electrical equipment and devices and to satisfy standards. However, many polymer flame resistance materials require a very high proportion of metal hydrate filler within the polymer matrix (60 wt%) to achieve a suitable level of flame resistance, which may lead to inflexibility, poor mechanical properties and problems during compounding and processing. In this study, the alumina trihydrate (ATH) was added to montmorillonite (MMT) as the halogen-free flame retardant of ethylene-vinyl acetate (EVA) copolymer, with various ratios of EVA/ATH/MMT. The prepared nanocomposites were characterized through various techniques of XRD, tensile test, DSC analysis, TGA, LOI evaluation, and FE-SEM to explore the effects of organic modified clay (OMMT) and the layer distance on the mechanical, thermal, and flame resistance properties. In the XRD examinations, the layer-distance of MMT increased from 1.27 to 1.96 nm when polymer was added to the octadecylamine modified MMT. The best tensile strength was obtained at 3 wt% MMT. In addition, the halogen-free flame resistance grade of EVA containing 3 wt% OMMT and 47 wt% ATH revealed the best elongation and fire resistance (LOI = 28). The tensile and flame resistance properties of the nanocomposites were also significantly improved.     

叔碳酸乙烯酯改性VAE乳液的研究

在VAE乳液生产工艺中引入改性单体叔碳酸乙烯酯,通过调整改性单体的加入量、选择合适的乳化剂和保护胶体的品种和用量,生产出符合DBJ/T01-63-2002《外墙外保温用聚合物砂浆质量检验标准》并适合喷雾干燥生产可再分散乳胶粉的三元共聚乳液。     

Effects of silicon additive as synergists of Mg(OH)2 on the flammability of ethylene vinyl acetate copolymer

The present work dealt with the effects of nine kinds of silicon additives on flame retardancy of ethylene‐vinyl acetate copolymer (EVA)/magnesium hydroxide [Mg(OH)₂] composites, as well as mechanical properties. The limiting oxygen index (LOI) test, horizontal fire test, vertical fire test, and cone calorimeter test were employed to evaluate flame retardancy of the composites. It was found that different silicon additives had different synergistic effects with Mg(OH)₂ on flame retardancy of the EVA matrix and exerted different influences on mechanical properties of the composites. The incorporation of organic montmorillonite (MMT) clay or silicone rubber not only made the composite reach FH‐1 rating in the horizontal fire test and FV‐1 rating in the vertical fire test, respectively, but also dramatically reduced the peak rate of heat release (Peak RHR) and increased the fire performance index (FPI) and ignition time (IT). The composites filled with precipitated SiO₂ exhibited the longest IT, the highest FPI, and FV‐1 rating. However, only the composites filled with silicone rubber could attain a balance between mechanical properties and flame retardancy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Study on the morphology and properties of metallocene polyethylene and ethylene/vinyl acetate blends

Two commercial polymer materials, metallocene linear low density polyethylene (m‐LLDPE) and ethylene/vinyl acetate copolymer (EVA) have been used to form binary blends of various compositions. The mechanical properties, morphology, rheological behavior, dynamic mechanical properties, and crystallization of m‐LLDPE/EVA blends were investigated. It was found that with the addition of EVA, the fluidity and processability of m‐LLDPE were significantly improved, and the introduction of polar groups in this system showed no significant changes in mechanical properties at lower EVA content. As verified by morphology observation and differential scanning calorimetry analysis, miscible blends were formed within certain weight ratios. Dynamic mechanical property studies showed that flexibility of the blends was enhanced in comparion with pure m‐LLDPE, where the peak value of loss modulus shifted to lower temperature and its intensity was enhanced as EVA content increased, indicating the existence of more amorphous regions in the blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 905–910, 2004     

The effect of isopropanol addition on enhancement of transdermal controlled release of ibuprofen from ethylene vinyl acetate copolymer membranes

This work reports the study of the addition of isopropanol on controlled release of ibuprofen from ethylene vinyl acetate (EVAc) copolymer membranes. An EVAc solution in cyclohexane (4% w/v) containing triethyl citrate (7% w/v) as plasticizer was mixed with ibuprofen at three different concentrations of 4, 6, and 8%. Isopropanol was mixed with each of the previous mixtures to form solutions of 1, 3, and 5% isopropanol concentrations. Samples were solvent cast on glass petri‐dishes to form membranes. Home‐made diffusion cells were used for in vitro study. These cells were composed of two compartments, donor (exposed to ambient conditions), and receptor (including buffer solution maintained at 37°C). Each cell was equipped with a sampling port and water in and out system. An ultraviolet spectrometer at 222 nm was used to measure release rates of obtained membranes. The diffusion mechanism for drug release was examined by zero‐order, first‐order, Higuchi and Korsmeyer‐Peppas theories to confirm the obtained membranes follow the matrix‐type system. By increasing the drug concentration from 4 to 8%, drug release (cumulative amount) was improved from 20 (47.5%) to 30 (36%) μg/cm² after 24 h. Addition of 5% isopropanol to the above samples (4 and 8% loading) further increased drug release to 24 and 43 μg/cm². Results were in good agreement with the Korsmeyer‐Peppas theory for samples with 4 (% w/w) of ibuprofen. The highest percentage of drug release after 24 h was 59% for the sample with 4% drug loading compared to 50% for the sample with 8% drug loading, both with 5% isopropanol. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of crystallinity and crosslinking on the thermal and rheological properties of ethylene vinyl acetate copolymer

Effects of crosslinking and crystallinity on the properties of the thermal and rheological properties of the EVA were studied. From the studies of storage modulus of the EVA with VA content in the solid temperature range (about −70 to 50 °C), the storage modulus decreased with increasing the VA content. This result suggested that the crystallinity of the EVA affected the storage modulus of the EVA because of the weak crosslinking of the EVA by DCP. From the studies of complex viscosity of the EVA with and without DCP in the melt state, the values of the power law parameter of the EVA without DCP ranged from 0.39 to 0.50 and the EVA with DCP ranged from 0.03 to 0.12. In the measurement of the complex viscosity of the EVA in the melt state, the crosslinking affected the complex viscosity of the EVA with DCP.     

Metal-phenolic networks: A biobased synergist for EVA/APP composites toward enhanced thermal stability and flame retardancy

In the present study, a biomass-derived metal-phenolic networks (MPN) were used as charring agent and flame-retardant synergist for Ethylene-vinyl acetate/Ammonium polyphosphate (EVA/APP) composites. Compared with the polyphenol, the thermal stability of MPN was improved remarkably, making it a good match for EVA. Meanwhile, Limit oxygen index test revealed that MPN endowed EVA/APP composites with enhanced flame-retardant performance. The reason on improvement in the flame retardancy of composites was also discussed and the corresponding mechanism was proposed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47243.     

Effects of compatibilizer on the layered silicate/ethylene vinyl acetate nanocomposite

Dispersion behavior of monmorillonite (MMT) is investigated in ethylene vinyl acetate (EVA)/MMT nanocomposite with various vinyl acetate content. Maleic anhydride (MAH) grafted polyethylenes with various MAH contents are used as a compatibilizer to enhance the dispersion of MMT. DMA and XRD studies indicate that an intercalated/exfoliated structure is obtained and vinyl acetate content and the concentration of PEMA play a critical role in EVA/MMT nanocomposite. Higher vinyl acetate content and concentration of grafted maleic anhydride result in better dispersion of MMT. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1057–1061, 2004     

Immiscible ethylene vinyl acetate and nylon blends processed below nylon melting temperature

This article focuses on unique compounding and processing conditions at a temperature slightly below the melting temperature of the dispersed phase and well above the melting peak temperature of the matrix. Compounding and processing were carried out at the same temperature. Fibrillar morphologies were obtained by blending ethylene vinyl acetate (EVA) copolymer with nylon 6 (N6) and compounding and processing them slightly below the N6 melting temperature. A hot, soft-solid particle drawing mechanism that operates in such processing conditions caused fibrillation of the N6 particles and formation of highly oriented fibril-filled composites throughout the entire volume. Morphological observations were made in the core region. Enhancement of some mechanical properties and interesting morphological structures were found in some of the blends. The melt elasticity, which was measured by the die swell of the filaments, was maximum at a temperature slightly below the N6 melting temperature, which supported the concept of fibrillation by processing it slightly below the melting temperature of the dispersed phase. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 661–671, 2001     

Investigation of flame retardancy and physical–mechanical properties of zinc borate/boric acid polyester composites

The glass fiber reinforced polyester composite materials were prepared with varying contents of boric acid, zinc borate, and magnesium hydroxide as flame retardants to improve the flame retardancy of the composites. Experimental results showed that boric acid exhibited a good flame retardant effect on the polyester composite. When boric acid content is used as 15 wt %, the Limiting Oxygen Index (LOI) value of the composite reached upto 25.3. The increase in boric acid content from 15 to 30 wt %, the LOI values of composite were enhanced from 25.3 to 34.5 by 9.2 units. The LOI values of the composite samples increased with increasing boric acid content. The smoke density results showed that the addition of glass fiber and flame retardants decreased the smoke density of the unreinforced polyester resin. The mechanical properties of the composites have decreased by the addition of flame retardants. The scanning electron micrographs taken from fracture surfaces were examined. The flame retardants, such as boric acid, were well dispersed in the glass fiber reinforced polyester composites and obviously improved the interfacial interaction between glass fibers and polyester composites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of expandable graphite on flame retardancy and thermal stability property of unsaturated polyester resins/organic magnesium hydroxide composites

An eco-friendly flame retardant unsaturated polyester resin (UPR) material was prepared by combination organic magnesium hydroxide (OMH) and expandable graphite (EG). Different from direct addition of magnesium hydroxide (MH) in UPR matrix-like traditional method, OMH as a reactive monomer participates in the polycondensation reaction of UPR was more effective in improving the compatibility of flame retardant with matrix. Interestingly, the flame retardant UPR composites exhibited a more satisfactory flame retardant effect when a certain amount of 8 wt % EG was added into UPR/OMH matrix because of the synergistic effect between OMH and EG, resulted in the limited oxygen index from 21.7 to 28.5% and UL-94 test passed V-0 rating. Moreover, the peak heat release rate, total heat release, and smoke production rate of flame retardant UPR composites significantly reduced. The excellent flame retardancy was due to the formation of a dense and continuous carbon layer in the later stages of combustion. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 47881.     

Synthesis of a bio-based triazine derivative and its effects on flame retardancy of polypropylene composites

A triazine derivative CC–Cy was synthesized using cytosine (Cy) and cyanuric chloride (CC). The CC–Cy was used as a charring agent and combined with ammonium polyphosphate (APP) to form an intumescent flame-retardant (IFR) system. The IFR system was applied to improve the flame retardancy of polypropylene (PP). Moreover, bisphenol-A bis(diphenyl phosphate) (BDP) was introduced in the IFR system to regulate the suitability between the IFR and PP. The results showed the PP containing 20 wt % APP and 5 wt % CC–Cy achieves the UL-94 V-2 rating. While the PP with 18 wt % APP/CC-Cy (4:1) and 3 wt % BDP obtains the UL-94 V-0 rating indicating the improved flame-retardant efficiency. Thermal degradation behaviors and char morphology both showed that the reactions between APP and CC–Cy promote the formation of char residues, and BDP works in gas phase to enhance the flame retardancy of PP composites. Thus, a synergistic IFR system based on APP, CC–Cy, and BDP is formed, which can protect PP from fire effectively. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 47367.     

甲基丙烯酸十六酯-醋酸乙烯酯的合成

以甲基丙烯酸十六酯和醋酸乙烯酯为原料,甲苯为溶剂,过氧化苯甲酰为催化剂,反应温度80～85℃,采用溶液聚合法合成甲基丙烯酸十六酯-醋酸乙烯酯聚合物。通过正交实验确定在反应单体甲基丙烯酸十六酯:醋酸乙烯酯的比例为2∶1,反应时间为5h,催化剂浓度为1.0%时为最佳反应条件。