Flame retardation of polypropylene: Effect of organoantimony compounds on the flammability and thermal behavior

Triphenylstibinedibromide and its derivatives with tribromo-, and pentachlorophenols have been used as flame-retardant additives for polypropylene. Maximum limiting oxygen index of 31.5 against 18.2 for unfilled polypropylene was obtained in a sample containing 10 phr of triphenylstibinedibromide. However, V-0 rating in UL-94 test was observed in 20 phr flame-retardant-filled polypropylene sample, while V-2 rating was obtained even at 5 phr flame-retardant level. Thermal behavior of flame-retardant-filled polypropylene was also studied in air atmosphere by thermogravimetric analysis, and an attempt has been made to correlate the flammability with the thermal behavior. The residue obtained in isothermal treatment at 450°C for 1/2 hour in air was analyzed for antimony and halogen which establishes the role of these flame retardants in vapor phase.     

The thermal expansion behaviour of oriented polypropylene

The thermal expansion behaviour of die drawn polypropylene rods has been measured over the temperature range −50°C to +10°C. For high draw samples the values for the thermal expansion coefficient in the axial direction α_∥ are negative and increase in magnitude with increasing temperature. It is shown that this result is consistent with the presence of an internal shrinkage stress. For low draw samples and most high draw samples after annealing, the value of α_∥ is positive and increases in magnitude with increasing temperature. It is shown that this result can also be explained in terms of an internal shrinkage stress, on the basis of a simple relationship between the axial and radial expansion coefficients.     

Halogeno‐modified polystyrene: monomer reactivity ratios,thermal behaviour and flammability

Chemical modification based on incorporation of flame retardants into polymer backbones was used in order to reduce flammability of polystyrene (PSt). The halogeno‐substituted styrenes: 4‐chlorostyrene (ClSt), 4‐bromostyrene (BrSt) and 2,3,4,5,6‐pentafluorostyrene (5FSt) were applied as reactive flame retardants. Homo‐ and copolymers of these halogeno‐substituted styrenes and styrene (St) were synthesized with various feed ratios using free radical bulk polymerization with azobisisobutyronitrile as a initiator. This yielded series of (co)polymers with various amounts of included ClSt, BrSt and 5FSt (5–50 mol% of modified St). Copolymer compositions were determined using ¹H NMR spectroscopy. The relative reactivity ratios of the used comonomers were determined by applying conventional linearization methods. The Jaacks (J) method was used for systems including BrSt and ClSt monomers whereas the Fineman–Ross method was additionally used to confirm the values of reactivity ratios of St–5FSt. The reactivity ratios of comonomer pairs obtained from J plots were 0.75 and 0.38 (St–ClSt), 1.65 and 0.46 (St–BrSt), 0.44 and 0.42 (St–5FSt). Glass transition temperature and thermal stability of obtained (co)polymers were determined using differential scanning calorimetry and thermogravimetric analysis (TGA), respectively. The thermal degradation kinetic of PSt, PClSt, PBrSt and P5FSt was studied applying TGA. Kinetic parameters such as thermal decomposition activation energy (E) and frequency factor (A) were estimated using Ozawa and Kissinger models. The resulting activation energies estimated using these two methods were quite close. The values of activation energy (kJ mol^?1) increased in the following order: PClSt (E(O) = 216.1) < PSt (E(O) = 219.9) < PBrSt (E(O) = 224.7) < P5FSt (E(O) = 330.9). A pyrolysis combustion flow calorimeter was applied as a tool for assessing the flammability of the synthesized (co)polymers. © 2014 Society of Chemical Industry     

Note: Effect of some halogenated flame retardants on the thermal characteristcs of selected tropical construction materials

The effects of some halogenated flame retradants (FR), sodium bromide and ammonium cupric chloride dihydrate (ACCD) on the thermal behaviour of roofing palm (Borassus aethiopun) and rattan palm (calamus deeratus) were studied. Their ignition time, flame propagation rate and afterglow time were investigated. No ignition occurred on the materials treated with 0.4M ACCD and no ignition was observed on roofing palm treated with 0.8M sodium bromide. Flame propagation rate and afterglow time were drastically reduced. Gravimetric analysis showed that these retardants acted by vapour phase and condensed phase mechanisms. An increase in char formation was also noted as a result of this treatment in all cases.     

Effect of polypropylene morphology on thermal cis-trans isomerization and photofading of some azo dyes: A kinetic study

Five polypropylene films were prepared having different crystallinity and morphology, the latter having been modified by stretching. They were colored with azo dyes XC₆H₄N?NC₆H₄N(C₂H₅)₂ (where X?H, OCH₃, CN, and NO₂). The kinetics of the thermal cis-trans isomerization of these dyes has been studied in the range 21–41°C, much above the glass transition temperature of the polymer. The isomerization process was found to be strictly first-order; the kinetic parameter values have been correlated with the free volume extent in the amorphous regions of the matrix. Lightfastness of the dyes in the polymer matrices has been also investigated: It appeared to be more important for the unoriented samples with respect to the stretched ones and substantially independent on the crystalinity degree.     

Photostabilizing effect of Ni(II) chelates in polymers. II. Effect of diamagnetic chelates on polypropylene phosphorescence

Examination of the phosphorescence emission form polypropylene shows the lifetime of the emission to be unaffected by a hydroxybenzophenone light stabilizer but significantly shorted by a diamagnetic Ni(II) chelate stabilizer.     

Synergistic effect of kaolinite/halloysite on the flammability and thermostability of polypropylene

Kaolinite (Kaol) and halloysite nanotubes (HNT) are both aluminosilicate clays with similar chemical formulation and different microshapes. In this article, nanotubular HNT and nanoplate Kaol together were introduced into polypropylene (PP) containing intumescent flame retardant (IFR). The flammability of the PP composites was characterized by limiting oxygen index (LOI), vertical burning (UL‐94), and cone calorimeter tests (CCT). The results showed that for the composite with 75 wt % PP and 25 wt % IFR, its LOI was 31.0% and it obtained a UL‐94 grade of V‐2. For the composite of 75 wt % PP, 23.5 wt % IFR, and 1.5 wt % (Kaol/HNT = 9/1), its LOI increased to 36.9 and it obtained a UL‐94 grade of V‐0; at the same time, its peak heat release rate value in CCT decreased by 82.2% compared to neat PP. The thermostability analysis indicated that the mixture of Kaol/HNT could improve the thermostability and final char yield. The char residues were comprehensively analyzed by scanning electron microscopy and Fourier transform infrared spectroscopy. The results illustrated that the Kaol/HNT combination was beneficial to forming a crosslinked network and promoting formation of a compact char with higher strength. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46507.     

Effect of aminobisphosphonated copolymer on the thermal stability and flammability of poly(methyl methacrylate)

Methyl methacrylate was copolymerized with propyl N,N‐tetramethylbis(phosphonate)‐bis(methylene)aminemethyl methacrylate (MAC₃NP₂). The thermal degradation and flammability of this modified poly(methyl methacrylate) (PMMA) were compared with those of pure PMMA using thermogravimetric analysis (TGA) and pyrolysis combustion flow calorimetry (PCFC). The morphology of char was investigated using scanning electron microscopy and the yield of phosphorus using energy‐dispersive X‐ray analysis. The gases evolved during degradation in TGA were analysed using Fourier transform infrared spectroscopy. The total heat release and heat release capacity of the reactively modified PMMA are reduced, as compared to pure PMMA. The modified PMMA presents a better thermal stability (above 290 °C) than pure PMMA and leads to an important char formation. A comparison among TGA, PCFC and the amount of phosphorus in the condensed phase gives useful information about the role of phosphorus in the flame retardancy of the copolymer. The result reveals the effect of phosphorus not only in the condensed phase but also in the vapour phase. Copyright © 2011 Society of Chemical Industry     

Effect of zeolite filler on the thermal degradation kinetics of polypropylene

In this study, the thermal degradation behavior of polypropylene (PP) and PP–zeolite composites was investigated. Clinoptilolite, a natural zeolitic tuff, was used as the filler material in composites. The effects of both pure clinoptilolite and silver‐ion‐exchanged clinoptilolite on the thermal degradation kinetics of the PP composites was studied with differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Polymer degradation was evaluated with DSC at heating rates of 5, 10, and 20°C/min from room temperature to 500°C. The silver concentration (4.36, 27.85, and 183.8 mg of Ag/g of zeolite) was the selected parameter under consideration. From the DSC curves, we observed that the heat of degradation values of the composites containing 2–6% silver‐exchanged zeolite (321–390 kJ/kg) were larger than that of the pure PP (258 kJ/kg). From the DSC results, we confirmed that the PP–zeolite composites can be used at higher temperatures than the pure PP polymer because of its higher thermal stability. The thermal decomposition activation energies of the composites were calculated with both the Kissinger and Ozawa models. The values predicted from these two equations were in close agreement. From the TGA curves, we found that zeolite addition into the PP matrix slowed the decomposition reaction; however, silver‐exchanged zeolite addition into the matrix accelerated the reaction. The higher the silver concentration was, the lower were the thermal decomposition activation energies we obtained. As a result, PP was much more susceptible to thermal decomposition in the presence of silver‐exchanged zeolite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 143–148, 2006     

Thermal and flammability properties of polypropylene/carbon nanotube nanocomposites

The thermal and flammability properties of polypropylene/multi-walled carbon nanotube, (PP/MWNT) nanocomposites were measured with the MWNT content varied from 0.5 to 4% by mass. Dispersion of MWNTs in these nanocomposites was characterized by SEM and optical microscopy. Flammability properties were measured with a cone calorimeter in air and a gasification device in a nitrogen atmosphere. A significant reduction in the peak heat release rate was observed; the greatest reduction was obtained with a MWNT content of 1% by mass. Since the addition of carbon black powder to PP did not reduce the heat release rate as much as with the PP/MWNT nanocomposites, the size and shape of carbon particles appear to be important for effectively reducing the flammability of PP. The radiative ignition delay time of a nanocomposite having less than 2% by mass of MWNT was shorter than that of PP due to an increase in the radiation in-depth absorption coefficient by the addition of carbon nanotubes. The effects of residual iron particles and of defects in the MWNTs on the heat release rate of the nanocomposite were not significant. The flame retardant performance was achieved through the formation of a relatively uniform network-structured floccule layer covering the entire sample surface without any cracks or gaps. This layer re-emitted much of the incident radiation back into the gas phase from its hot surface and thus reduced the transmitted flux to the receding PP layers below it, slowing the PP pyrolysis rate. To gain insight into this phenomena, thermal conductivities of the nanocomposites were measured as a function of temperature while the thermal conductivity of the nanocomposite increases with an increase in MWNT content, the effect being particularly large above 160 °C, this increase is not as dramatic as the increase in electrical conductivity, however.     

Effect of isomerization on thermal behaviour of bisitaconimides

The effect of isomerization of N,N′‐bisitaconimido‐4,4′‐diphenyl ether to the corresponding biscitraconimide on the curing characteristics and thermal stability of cured resins is described. Resins having bisitaconimide:biscitraconimide ratios of 23:77–93:7 were prepared by reacting 4,4′‐diaminodiphenyl ether with itaconic anhydride in solvents of different polarities and under different reaction conditions. Resins containing a higher proportion of citraconimide had a lower melting point (191 vs 208 °C). The curing exotherm was observed immediately after melting in all the resins and exothermic peak temperature reduced with increase in citraconimide content. Resins having a higher proportion of citraconimide on isothermal curing (200 °C, 2 h) and subsequent heating in nitrogen atmosphere degraded at a slightly lower temperature. However, the char yield at 800 °C did not show any systematic dependence on citraconimide content. © 2002 Society of Chemical Industry     

Crystallization and thermal behaviour of isotactic polypropylene blended with an alicyclic random co-oligomer

A fully saturated, alicyclic hydrocarbon resin (IST) was blended with isotactic polypropylene (iPP). IST is a random co-oligomer of low average molecular weight obtained by oligomerization of indene, α-methyl styrene and vinyl toluene, followed by hydrogenation. The crystallization and thermal behaviour of iPP/IST blends were analyzed by microscopy and differential scanning calorimetry (DSC). The influence of blend composition on the spherulite growth rate and on the overall crystallization rate suggests that the two components form a miscible blend in the amorphous phase, as confirmed by the following observations: All blends show a single glass transition temperature (Tg); its value, depending on composition, lies between the iPP and IST Tg values (–14°C and 82°C, respectively), and is in good agreement with the theoretical values calculated by the Fox equation. The equilibrium melting temperature calculated for pure iPP was equal to 187°C; this value decreases with blending to 175°C for the iPP/IST 50/50 (w/w) blend. The χ₁₂ parameter of the iPP/IST system was equal to ?0.435, the negative value should suggest that the two components can form a compatible mixture which is thermodynamically stable above the equilibrium melting temperature.     

Influence of nano silica hybrid expandable graphite on flammability,thermal stability,and mechanical property of polypropylene/polyamide 6 blends

Silica (SiO₂) nanohybrid expandable graphite (nEG) particles fabricated through one-step method are used as an efficient flame retardant for polypropylene (PP)/polyamide 6 (PA6) blends. The effect of nEG on the flammability, thermal stability, crystallization behaviors, and mechanical properties of PP/PA6 composites is investigated by using limit oxygen index (LOI), UL-94 test, cone calorimeter test (CCT), thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared, scanning electron microscopy, and mechanical tests. Compared with pure expandable graphite (EG), nEG improves the flame retardancy of composites. The results of LOI show that LOI of PP/PA6/nEG10 and PP/PA6/nEG15 composites are 26.0% and 27.2%, respectively. But the LOI values of PP/PA6/EG10 and PP/PA6/EG15 composites are 25.7% and 26.9%, respectively. The UL-94 test results show that PP/PA6/nEG10 composites reach V-1 level when the nEG content is only 10%. However, the PP/PA6 composites with 10% EG does not pass the UL-94 test. In addition, PP/PA6 composites with 15% nEG can reach V-0 level. The CCT results further show that nEG has a higher flame-retardant efficiency than pure EG for PP/PA6 blends. The thermal stability of PP/PA6/nEG composites is better than that of PP/PA6/EG composites. The mechanical property tests indicate that nEG is more conducive to maintain the tensile and impact strengths of PP/PA6 blends than EG due to the enhanced compatibility and interfacial adhesion.     

Effect of various triazine derivatives on the thermal oxidative degradation of isotactic polypropylene

A number of triazine derivatives, mostly aryloxy-s-triazines, were prepared, and the effects of these compounds on the thermal oxidative degradation of isotactic polypropylene were examined by conventional oxygen uptake. Almost all triazine derivatives prepared showed a more or less inhibitive effect on the degradation of the polymer. Among them, α- and β-napthyloxy-s-triazines were found to be excellent inhibitors. On the basis of the results obtained, the relationship between inhibitive effect and the structure of the triazine derivatives is discussed.     

Effect of structure on the thermal behaviour of ethynyl-terminated imide resins

A series of ethynyl-terminated aromatic imide monomers containing phosphine oxide in the backbone were synthesized by the reaction of tris(3-aminophenyl) phosphine oxide (TAP) or bis(3-aminophenyl)methyl phosphine oxide (BAP) with pyromellitic dianhydride (PMDA) or 3, 3′,4, 4′-benzophenone tetracarboxylic acid dianhydride (BTDA) or 4, 4′-perfluoroisopropylidenebis(phthalic anhydride), and 3-ethynyl aniline. Structural characterization was done by infrared, nuclear magnetic resonance spectroscopy and elemental analysis. Thermal characterization was done by differential scanning calorimetry and thermogravimetric analysis. The decomposition temperatures of cured resins were above 500°C in nitrogen atmosphere. Char yield at 800°C ranged from 52–63.5%.     

Effect of hybrid filler (HNTs‐phthalocyanine) on the thermal properties and flammability of diene rubber

Rubber is an essential polymer widely used in the auto‐industry. We report a method for the synthesis of zinc phtalocyanine (ZP), chloroalumino phthalocyanine (CP), and their hybrid fillers obtained by the synthesis of the two phtalocyanines in the presence of halloysite nanotubes (HNTs). The hybrid fillers were characterized by means of microscopic, thermal, and particle size measurement analysis. The effect of these fillers on the properties of diene rubbers were assessed in comparison with a physical mixture of halloysite and ZP or CP pigment. The dispersion degree of hybrid fillers inside an elastomeric matrix (rubber) was assessed with the atomic force microscopy. The influence of the hybrid fillers on the thermal and mechanical properties and flammability of butadiene‐acrylonitrile (NBR) and butadiene‐styrene (SBR) rubbers was assessed by analyzing the measurement results obtained by means of thermogravimetric analysis, differential scanning calorimetry, Zwick Tensile testing, FAA micro‐calorimeter, and oxygen index determination. We found that regardless of the spatial network structure of NBR and SBR rubbers, the incorporation of hybrid fillers into the matrix of the elastomers showed an improvement in their thermal and mechanical properties as well as a significant reduction in flammability. The improvement is attributed to the smaller size and much better dispersion of HZ and HC in relation to the particles of phthalocyanine. The colored composites of NBR rubber, containing hybrid filler (HZ or HC), showed an increase in the heat capacity compared to the uncolored samples, which can increase safety by facilitating the processes of self‐extinguishing. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42593.     

Effect of hydrothermally synthesized titanium nanotubes on the behaviour of polypropylene for antimicrobial applications

TiO₂ nanotubes (TiO₂‐Ntbs) synthesized by a hydrothermal method were used as filler to prepare polypropylene (PP) composites by melt blending. Their structural properties as well as their biocidal potential were studied. Nanotubes were used either as‐synthesized or organically modified with hexadecyltrimethoxysilane (Mod‐TiO₂). These nanoparticles form secondary structures with sizes around 100 nm that are well dispersed in the polymer matrix, but not homogeneously because agglomerates larger than 1 µm are also seen by transmission electron microscopy. Regarding the properties of the composites, the incorporation of the nanoparticles increased the polymer's crystallinity and thermal stability. The maximum decomposition temperature of the matrix increased by ca 13 °C compared to virgin PP. The nanotubes further increase the spherulite nucleation density, and therefore a reduction in the diameter of spherulites and an increase in their number were observed. Despite the above, the addition of TiO₂ nanoparticles did not modify the mechanical properties of PP. The PP/TiO₂‐Ntb nanocomposites exposed to UVA radiation showed a biocidal behaviour, reducing a colony of Escherichia coli by 81%. © 2015 Society of Chemical Industry