Profluorescent nitroxides: Thermo-oxidation sensors for stabilised polypropylene

The profluorescent nitroxide, 1,1,3,3-tetramethyldibenzo[e,g]isoindolin-2-yloxyl (TMDBIO) was investigated as a probe for the radical-mediated degradation of stabilised polypropylene. TMDBIO has been previously shown to be a sensitive probe for free-radical degradation during the thermo-oxidation of unstabilised polypropylene. Here we report on the effect that adding hindered phenol or phosphite stabilisers to polypropylene has on the free-radical sensing ability of TMDBIO during thermo-oxidation. In addition, novel dual-functional, hindered phenol containing profluorescent nitroxides, 5-[2-(4-hydroxy-3,5-di-tert-butylphenyl)ethenyl]-1,1,3,3-tetramethylisoindolin-2-yloxyl (HSTMIO) and its derivatives were investigated as probes for the radical-mediated degradation of polypropylene. These dual-functional probes were shown to be efficient stabilisers for polypropylene during thermo-oxidation at 150 °C in oxygen and sensors of thermo-oxidation during its early stages, in the so-called “induction period”.     

Thermal degradation analysis and XRD characterisation of fibre-forming synthetic polypropylene containing nanoclay

Flammability of synthetic fibres is significantly worse than that of bulk polymers because of the high surface area to volume ratio and the low tolerance to high filler loadings in the fibre production process. Introducing nanocomposite structures has the potential to enhance the char formation at relatively low loadings of nanoparticulate fillers and hence can reduce the flammability of synthetic polymers and fibres.This paper reports thermal degradation analysis results in conjunction with TG analysis under different atmospheres and further studies of X-ray diffraction characterisation of fibre-forming polypropylene containing selected dispersed nanoclays.The concentrations of hydrocarbons, carbon monoxide and carbon dioxide released during the TG analysis have been monitored and analysed by using a combined electrochemical infrared analyser. The intensity changes of the crystallinity peaks and nanoclay peaks in the polymer and composites are discussed.     

Flammability and thermal degradation of flame retarded polypropylene composites containing melamine phosphate and pentaerythritol derivatives

The flammability of polypropylene (PP) composites containing intumescent flame retardant additives, i.e. melamine phosphate (MP) and pentaerythritol (PER), dipentaerythritol (DPER) or tripentaerythritol (TPER) was characterized by limiting oxygen index (LOI), UL 94 and the cone calorimeter, and the thermal degradation of the composites was studied using thermogravimetric analysis (TG) and real time Fourier transform infrared (RTFTIR). It has been found that the PP composite containing only MP does not show good flame retardancy even at 40% additive level. Compared with the PP/MP binary composite, the LOI values of the PP/MP/PER (PP/MP/DPER or PP/MP/TPER) ternary composites at the same additive loading are all increased, and UL 94 ratings of most ternary composites studied are raised to V-0 from no rating (PP/MP). The cone calorimeter results show that the heat release rate and smoke emission of some ternary composites decrease in comparison with the binary composite. It is noted from the TG data that initial decomposition temperatures of ternary composites are lower than that of the binary composite. The RTFTIR study indicates that the PP/IFR composites have higher thermal oxidative stability than the pure PP.     

Flammability of wood-polypropylene composites

Addition of wood particles to polymers can cause a change of properties of the composites which depends on features of lignocellulosic materials and those of polymers. It is also observed in the flammability characteristics of the composites.In this work, the flammability of polypropylene composites with pine wood particles obtained by extrusion and press moulding was analyzed. The amount of wood particles was 50%. Polymers with various melt flow index (MFI) were used (Malen F-401, PP HY-202 and Malen S-702).The samples were tested using Cone Calorimeter at heat flux of 35 kW/m². Heat release rate (HRR) curves of composites show that thermal decomposition depends on the kind of polypropylene used. In the presence of PP HY-202 and Malen S-702, the flammability characteristic is similar to that of lignocellulosic materials, in contrast to composites with matrices prepared from Malen F-401. The observed phenomenon is interpreted in terms of the wettability of particles of pine wood by polymers of varying melt viscosity.     

Flammability, structure and mechanical properties of PP/OMMT nanocomposites

Polypropylene/organoclay (PP/OMMT) nanocomposites were prepared in a twin-screw corotating extruder using two methods. The first method was the dilution of commercial (PP/50% Nanofil SE3000) masterbatch in PP (or PP with commercial flame retardant). The second method consists of two stages was the extrusion of maleic anhydride grafted polypropylene (PP-g-MAH) with commercially available organobentonite masterbatch in first stage and dilution of the masterbatch in PP (or PP with commercial flame retardant) in second stage. XRD results showed no intercalation in composites obtained from commercial masterbatch without compatibilizer and semi - delamination for compatibilized systems. Tensile tests revealed that nanocomposites with 5% of organoclay have a slightly higher tensile modulus and tensile strength than pristine PP, however addition of the commercial flame retardant (FR) reduces mechanical parameters to roughly the level of those for neat PP. PP/OMMT composites have approx. 25% higher oxygen index than pristine PP, and this changes slightly after the addition of FR. The cone calorimeter tests showed a decrease of a heat release rate (HRR) and a mass loss rate (MLR) after the addition of FR.     

A comprehensive study of the synergistic flame retardant mechanisms of halloysite in intumescent polypropylene

This work aims to evaluate the efficiency of halloysite as synergistic agent in an intumescent PP system based on a coated ammonium polyphosphate (IFR). The first part of the study analyses the thermal stability and fire performance of PP when using the intumescent formulation alone or in combination with the aluminosilicate nanotubes (HNTs). Cone calorimetry reveals that partial substitution of IFR by HNTs (3 wt.%) imparts substantial improvement in flame retardancy with reduced heat release rate and longer burning times. Additionally, a shift from V-1 to V-0 classification is achieved at the UL-94 test with only 1.5 wt.% HNTs. The second part provides a better understanding of the physical and chemical mechanisms of action of HNTs in the intumescent systems. The chemical evolution of the condensed phase during combustion is described by solid state NMR, and in particular using 2D NMR. Results indicate that halloysite speeds up the development of the intumescent shield, but also enhances its mechanical properties by physical reinforcement (i.e. aluminosilicate “skeleton-frame” for the phospho-carbonaceous structure) and/or by chemical interactions with IFR yielding to aluminophosphates. These new chemical species allow thermal stabilization of the char at high temperatures and provide good macro- and micro-structural properties. Both effects increase the mechanical strength of the protective layer during burning ensuring excellent heat and mass transfer limitations between gas and condensed phases.     

The influence of KH-550 on properties of ammonium polyphosphate and polypropylene flame retardant composites

Ammonium polyphosphate (APP)/polypropylene (PP) composites were prepared by melt blending and extrusion in a twin-screw extruder. APP was first modified by a silane coupling agent KH-550 then added to polypropylene. The surface modification of APP by the coupling agent decreased its water solubility and its interface compatibility with the PP matrix. Limiting oxygen index (LOI) and thermogravimetric analysis (TGA) were used to characterize the flame retardant property and the thermal stability of the composites. The addition of APP improved the flame retardancy of PP remarkably. The crystal structures of APP/PP composites were characterized by X-ray diffraction (XRD). The results indicated that β-crystal phase PP may be formed. The structures and morphologies of APP, KH-550/APP and APP/PP composites were characterized by field-emission scanning electron microscope (FESEM). The mechanical property tests showed good mechanical properties of composite materials. Compared with unmodified one, the impact strength, tensile strength and elongation of modified APP/PP were all improved.     

Flammability characteristics and flame retardant mechanism of phosphate-intercalated hydrotalcite in halogen-free flame retardant EVA blends

The flammability characteristics and flame retardant mechanism of phosphate-intercalated hydrotalcite (MgAl-PO₄) in the halogen-free flame retardant ethylene vinyl acetate (EVA) blends have been studied by X-ray diffraction (XRD), Fourier transfer infrared (FTIR) spectroscopy, cone calorimeter test (CCT), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), limiting oxygen index (LOI) and UL-94 tests. The results show that the hydrotalcite MgAl-PO₄ intercalated by phosphate possesses the enhanced thermal stability and flame retardant properties compared with ordinary carbonate-intercalated hydrotalcite MgAl-CO₃ in the EVA blends. The CCT tests indicate that the heat release rate (HRR) and mass loss rate (MLR) values of the EVA/MgAl-PO₄ samples are much lower than those of the EVA/MgAl-CO₃ samples. The TGA data show that the thermal degradation rates of MgAl-PO₄ and EVA/MgAl-PO₄ samples are much slower and leave more charred residues than those of MgAl-CO₃ and its corresponding EVA blends. The LOI values of EVA/MgAl-PO₄ samples are 2% higher than those of the corresponding EVA/MgAl-CO₃ samples at the range of 40–60 wt% loadings, while the EVA sample with 55 wt% MgAl-PO₄ can reach the UL-94 V-1 rating. The dynamic FTIR spectra reveal that the flame retardant mechanism of MgAl-PO₄ can be ascribed to its catalysis degradation of the EVA resin, which promotes the formation of charred layers with the P–O–P and P–O–C complexes in the condensed phase. The SEM observations give further evidence of this mechanism that the compact charred layers formed from the EVA/MgAl-PO₄ sample effectively protect the underlying polymer from burning.     

STUDY ON THE PHOTOLYSIS MECHANISM OF POLYESTER FROM SUCCINIC ACID AND N-β-HYDROXYETHYL 2,2,6,6-TETRAMETHYL,4-HYDROXY PIPERIDINE (TINUVIN-622)

The photolysis mechanism of polyester of succinic acid with N—β-hydroxyethyl 2,2,6,6-tetramethyl-4-hydroxy piperidine (Tinuvin-622) has been studied by instrumental analysis. The results show that Tinuvin-622 can be easily photolysed. Based on the results of IR, NMR, ESR, GPC, GC, MS, the photolysis mechanism of Tinuvin-622 has been proposed.     

Flammability characteristics and synergistic effect of hydrotalcite with microencapsulated red phosphorus in halogen-free flame retardant EVA composite

The flammability characteristics and synergistic effect of hydrotalcite with microencapsulated red phosphorus (MRP) in halogen-free flame retardant ethylene vinyl acetate (EVA) composite have been studied by cone calorimeter test (CCT), thermogravimetric analysis (TGA), limiting oxygen index (LOI) and UL-94 test. The results obtained by comparing the flame retardancy of hydrotalcite with magnesium hydroxide (MH) and aluminium hydroxide (AH) for their EVA composites showed that hydrotalcite has higher flame retardant effect than MH and AH at the same loading level. The CCT tests indicated that the heat release rate (HRR) and mass loss rate (MLR) of EVA composite blended with hydrotalcite greatly decreased compared with those blended with MH and AH. The LOI values of EVA/hydrotalcite composites are 3-4% higher than those of the corresponding MH composites at 40-60 wt% loading levels, and 6% higher than that of the corresponding AH composite at 40 wt% loading level. Moreover, the addition of a given amount of MRP apparently resulted in the increase of LOI value and decrease of the HRR and MLR as well the loading of hydrotalcite in EVA blend while keeping the V-0 rating in UL-94 test. However, the smoke release increased during the combustion of EVA/hydrotalcite blend containing MRP.     

Morphological and structural characterization of polypropylene/conductive graphite nanocomposites

The structure and morphology of polypropylene/conductive graphite (PP/CG) composites were studied by wide angle X-ray diffraction, small-angle X-ray scattering and scanning electron microscopy. An effect of graphite on the crystallization behavior was observed and the opposite influences of enhanced thermal conductivity and hinder of chain mobility on the formation of the γ-phase of PP were discussed.     

Characterising in situ activation and degradation of hindered amine light stabilisers using liquid extraction surface analysis-mass spectrometry

Changes in the molecular structure of polymer antioxidants such as hindered amine light stabilisers (HALS) is central to their efficacy in retarding polymer degradation and therefore requires careful monitoring during their in-service lifetime. The HALS, bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (TIN123) and bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (TIN292), were formulated in different polymer systems and then exposed to various curing and ageing treatments to simulate in-service use. Samples of these coatings were then analysed directly using liquid extraction surface analysis (LESA) coupled with a triple quadrupole mass spectrometer. Analysis of TIN123 formulated in a cross-linked polyester revealed that the polymer matrix protected TIN123 from undergoing extensive thermal degradation that would normally occur at 292 °C, specifically, changes at the 1- and 4-positions of the piperidine groups. The effect of thermal versus photo-oxidative degradation was also compared for TIN292 formulated in polyacrylate films by monitoring the in situ conversion of N-CH₃ substituted piperidines to N-H. The analysis confirmed that UV light was required for the conversion of N-CH₃ moieties to N-H – a major pathway in the antioxidant protection of polymers – whereas this conversion was not observed with thermal degradation. The use of tandem mass spectrometric techniques, including precursor-ion scanning, is shown to be highly sensitive and specific for detecting molecular-level changes in HALS compounds and, when coupled with LESA, able to monitor these changes in situ with speed and reproducibility.     

Synergistic effect of nanoflaky manganese phosphate on thermal degradation and flame retardant properties of intumescent flame retardant polypropylene system

Nanoflaky manganese phosphate (NMP) was synthesized from manganese nitrate and trisodium phosphate dodecahydrate, and used as a synergistic agent on the flame retardancy of polypropylene (PP)/intumescent flame retardant (IFR) system. The thermogravimetric analysis (TGA), real time Fourier-transform infrared (RTFTIR) spectroscopy measurements, cone calorimeter (CONE) and microscale combustion calorimeter (MCC) were used to evaluate the synergistic effects of NMP on PP/IFR system. When IFR + NMP was fixed at 20 wt% in flame retardant PP system, the TGA tests showed that NMP could enhance the thermal stability of PP/IFR system at initial temperature from about room temperature to 440 °C and effectively increase the char residue formation. The RTFTIR results revealed that NMP could clearly change the decomposition behavior of PP in PP/IFR system, which promotes decomposition at the initial temperature from about room temperature to 260 °C and forms more effective barrier layer to protect PP from decomposing at high temperature from about 260 °C to 500 °C. The CONE tests indicated that the addition of NMP in PP/IFR system not only reduced the peak heat release rate (HRR), but also prolonged the ignition time. The MCC results revealed that PP/IFR/NMP system generated less combustion heat over the course of heating than that of PP/IFR system. And scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were used to explore the char residues of the PP/IFR systems with and without NMP.     

Synthesis of a novel ionic liquid containing phosphorus and its application in intumescent flame retardant polypropylene system

A novel ionic liquid containing phosphorus ([PCMIM]Cl) was synthesized and characterized by FTIR, ¹H NMR, ¹³C NMR and ³¹P NMR. Moreover, a new intumescent flame retardant (IFR) system, which was composed of [PCMIM]Cl and ammonium polyphosphate (APP), was used to impart flame retardancy and dripping resistance to polypropylene (PP). The flammability and thermal behaviors of intumescent flame‐retarded PP (PP/IFR) composites were evaluated by limiting oxygen index (LOI), UL‐94 test, thermogravimetric analysis (TGA) and cone calorimeter test. It was found that there was an obvious synergistic effect between [PCMIM]Cl and APP. When the weight ratio of [PCMIM]Cl and APP was 1:5 and the total amount of IFR was kept at 30 wt%, LOI value of PP/IFR composite reached 31.8, and V‐0 rating was obtained. Moreover, both the peak heat release rate and the peak mass loss rate of PP/IFR composites decreased significantly relative to PP and PP/APP composite from cone calorimeter analysis. The TGA curves suggested that [PCMIM]Cl had good ability of char formation, and when combined with APP, it could greatly promote the char formation of PP/IFR composites, hence improved the flame retardancy. Additionally, the rheological behaviors and mechanical properties of PP/IFR composites were also investigated, and it was found that [PCMIM]Cl could also serve as an efficient lubricant and compatibilizer between APP and PP, endowing the materials with satisfying processability and mechanical properties. Copyright © 2013 John Wiley & Sons, Ltd.     

Stabilization of γ-sterilized biomedical polyolefins by synergistic mixtures of oligomeric stabilizers. Part II. Polypropylene matrix

In our previous study we have found the synergistic combinations of stabilizers which follow different mechanisms of stabilization and are approved for food contact and biomedical applications. The present attempt is to test the potentials of those systems in stabilizing γ-sterilized isotactic polypropylene (i-PP). Isotactic polypropylene was melt-mixed with hindered amine stabilizers (HAS), phenolic antioxidants and organo-phosphites (hydroperoxide decomposer) and sterilized with different doses of γ-radiation. Stabilization was monitored in terms of changes in the functional groups (oxidation products), tensile properties, yellowing and surface morphology by FTIR spectroscopy, Instron, colorimetry (reflectance) and scanning electron microscopy (SEM), respectively. The trend in stabilizing the efficiency of binary (1:1), ternary (1:1:1) and quaternary (1:1:1:1) additive systems was confirmed by comparing the stabilizing efficiency of mixtures with and without phenol system as well as with their counter parts of EP copolymer matrix. The binary system of secondary HAS and tertiary HAS, has shown antagonistic effect of stabilization whereas their combination with organo-phosphite has exhibited synergistic effect even at higher doses of γ-sterilization. Due to the oxidation of hindered phenol, phenol systems have shown discoloration and it was reduced by mixing with secondary HAS, tertiary HAS and organo-phosphite. The response of the stabilizer systems is better to ethylene-propylene (EP) copolymer than to i-PP in terms of stabilization.     

Effect of a novel charring-foaming agent on flame retardancy and thermal degradation of intumescent flame retardant polypropylene

A new triazine polymer was synthesized by using cyanuric chloride, ethanolamine and ethylenediamine as raw materials. It is used both as a charring agent and as a foaming agent in intumescent flame retardants, designated as charring-foaming agent (CFA). Effect of CFA on flame retardancy, thermal degradation and mechanical properties of intumescent flame retardant polypropylene (PP) system (IFR-PP system) has been investigated. The results demonstrated that the intumescent flame retardant (IFR) consisting of CFA, APP and Zeolite 4A is very effective in flame retardancy of PP. It was found that when the weight ratio of CFA to APP is 1:2, that is, the components of the IFR are 64 wt% APP, 32 wt% CFA and 4 wt% Zeolite 4A, the IFR presents the most effective flame retardancy in PP systems. LOI value of IFR-PP reaches 37.0, when the IFR loading is 25 wt% in PP. It was also found that when the IFR loading is only 18 wt% in PP, the flame retardancy of IFR-PP can still pass V-0 rating, and its LOI value reaches 30.2. TGA data obtained in pure nitrogen demonstrated that CFA has a good ability of char formation itself, and CFA shows a high initial temperature of the thermal degradation. The char residue of CFA can reach 35.7 wt% at 700 °C. APP could effectively promote the char formation of the APP-CFA system. The char residue reaches 39.7 wt% at 700 °C, while it is 19.5% based on calculation. The IFR can change the thermal degradation behaviour of PP, enhance T_max of the decomposition peak of PP, and promote PP to form char, based upon the results of the calculation and the experiment. This is attributed to the fact that endothermic reactions took place in IFR charring process and the char layer formed by IFR prevented heat from transferring into inside of IFR-PP system. TGA results further explained the effective flame retardancy of the IFR containing CFA.     

Flammability characterization and effects of magnesium oxide in halogen-free flame-retardant EVA blends

The effects of magnesium oxide(Mg O) on the flame retardant performance of intumescent systems based on ammonium polyphosphate(APP) and pentaerythritol(PER) in ethylene vinyl acetate copolymer(EVA) were studied. The results showed that Mg O affects both the quality and quantity of residual char. There is an optimal value for the loading amount of Mg O. More or less Mg O loading may cause the formation of defective char layers and worsen the flame retardancy of EVA. According to the results of limiting oxygen index(LOI), vertical flammability test(UL94 rating) and cone calorimetry(CONE), the best flame retardancy with a strong and well intumescent char is obtained from the sample with 1 wt% of Mg O, which has the highest LOI value of 27.9, UL94 rating of V-0 and the lowest peak heat release rate of 242 k W·m?2.     

Flammability, microhardness and transparency of nanocomposites based on functionalized polyethylenes

The flammability, microhardness and transparency of nanocomposites based on poly(ethylene-co-acrylic acid) copolymers having different concentration of acrylic acid and different molar mass, their Zn ionomer and ethylene-glycidylmethacrylate copolymer as matrixes and on organically modified montmorillonite as a nanofiller have been investigated. The presence and the increase in the content of the clay lead to the increase in the limiting oxygen index and to significant reduction of the burning rate of all materials. The results from the Vickers microhardness measurements have shown that the addition of the clay to matrixes of polar functionalized polyethylenes leads to a significant increase in the microhardness of the materials, while the creep constant does not decrease significantly. The UV spectra show that the light transmittance of the materials does not change significantly in the presence of the clay, i.e., the nanocomposite films preserve the polymer transparency. The results have been interpreted by the intercalated structures of the nanocomposites investigated.     

Photo-stability of yellow-green emitting 1,8-naphthalimides containing built-in s-triazine UV absorber and HALS fragments and their acrylonitrile copolymers

Two novel 1,8-naphthalimide dyes, containing active fragments of both 2-(2-hydroxyphenyl)-1,3,5-triazine UV absorber and 2,2,6,6-tetramethylpiperidine radical scavenger as well as a polymerisable allyl group, were designed as multifunctional yellow-green emitting fluorophores capable simultaneously of chemically fluorescent dyeing and photo-stabilisation of polymers. Their basic photo-physical characteristics have been determined and are discussed. It was shown that combination of different structural units in the 1,8-naphthalimide molecule does not result in their interaction through intramolecular fluorescence quenching due to an electronic energy transfer. The ability of the combined dyes to copolymerise with acrylonitrile was demonstrated as polyacrylonitriles stable to solvents and with an intense colour and fluorescence were obtained. Photo-degradation of the new fluorophores and their influence on the photo-stability of the coloured copolymers have been studied and compared to other similar fluorescent dyes, not containing either UV absorber or hindered amine fragment in their molecules as well as not containing both of them. Novel fluorophores showed the best photo-stability in both solution and polymer. A significant photo-stabilising effect towards photo-destruction of polyacrylonitrile was found, which might be caused by a possible “synergism” of two stabiliser fragments differing in their action.     

Flame retardant mechanism of an efficient flame-retardant polymeric synergist with ammonium polyphosphate for polypropylene

An efficient flame retardant polymeric synergist poly[N⁴-bis(ethylenediamino)-phenyl phosphonic-N², N⁶-bis(ethylenediamino)-1,3,5-triazine-N-phenyl phosphonate] (PTPA) was designed and synthesized from cyanuric chloride, ethylenediamine and phenylphosphonic dichloride. It was characterized by Fourier Transform Infrared (FTIR), ¹H NMR and ³¹P NMR, Elemental Analysis (EA) and Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). Combined with ammonium polyphosphate (APP), a new intumescent flame retardant (IFR) was obtained. The flammability behaviors of polypropylene (PP)/IFR system were investigated by limiting oxygen index (LOI), vertical burning test (UL-94) and cone calorimetry. With 25 wt% of IFR (APP:PTPA = 2:1), the PP/IFR system could achieve a LOI value of 34.0% and UL-94 V-0 rating, and the heat release rate (HRR), peak heat release rate (PHRR), total heat release (THR) and smoke production rate (SPR) were considerably reduced, especially HRR and SPR were decreased by 85% and 79%, respectively. The results indicate that there is an excellent synergism between APP and PTPA, which endows PP with both good flame retardancy and good smoke suppression. Furthermore, the thermal degradation mechanism of IFR and the flame-retardant mechanism of PP/IFR system were investigated by thermogravimetric analysis (TGA), FT-IR, TG-FTIR and scanning electron microscope (SEM). The study on the flame-retardant mechanism of IFR indicated that a structure containing –CN was formed due to the reaction between APP and PTPA.