Effect of a novel phosphorous-nitrogen containing intumescent flame retardant on the fire retardancy and the thermal behaviour of poly(butylene terephthalate)

A novel phosphorus-nitrogen containing intumescent flame retardant (P-N IFR) was prepared via the reaction of a caged bicyclic phosphorus (PEPA) compound and 4,4′-diamino diphenyl methane (DDM) in two steps. The product was added to poly(butylene terephthalate) (PBT) to obtain halogen-free flame retarded polyester. UL-94 test, thermogravimetry and in situ infrared spectroscopy were used to characterize the flammability, thermal degradation properties and the char-forming process. It was shown that the phosphorus-nitrogen containing compound could improve both the flame retardancy and thermal stability more effectively than other P-N flame retardants. Furthermore, it was a good char-forming agent incorporated with the co-addition of polyurethane (PU) when the combustion occurred. The formation of P-N structure was incorporated in the char layer.     

Synthesis of a phosphinated acetoxybenzoic acid and its application in enhancing Tg and flame retardancy of poly(ethylene terephthalate)

A new phosphinated acetoxybenzoic acid, 1‐(4‐acetoxyphenyl)‐1‐(4‐carboxylphenyl)‐1‐(6‐oxido‐6H‐dibenz<c,e><1,2> oxaphosphorin‐6‐yl)ethane (3), was prepared by a three‐step procedure. Phosphinated copolyesters based on the acidolysis and polycondensation of (3) with poly(ethylene terephthalate) (PET) were prepared. The crystallinity of copolyesters decreased gradually with the content of (3), as shown in wide‐angle X‐ray diffractograms and differential scanning calorimetry thermograms. Dynamic mechanical analysis and thermal mechanical analysis show T_g increased with the content of (3). UL‐94 flame retardant test shows that the flame resistance of PET was enhanced with the content of (3), and a copolyester with UL‐94 V‐0 grade can be achieved with a phosphorus content as low as 1.43 wt %. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 424–434     

The impact of resorcinol bis(diphenyl phosphate) and poly(phenylene ether) on flame retardancy of PC/PBT blends

Flame retardancy of bisphenol A polycarbonate (PC)/poly(butylene terephthalate) (PBT) blends was improved by the addition of resorcinol bis(diphenyl phosphate) (RDP) and poly(phenylene ether) (PPO). A PC/PBT blend at 70/30 weight ratio obtained a V‐0 rating by the addition of 10 wt% RDP and 10 wt% PPO. The combination of 5 wt% methyl methacrylate‐butadiene‐styrene tercopolymer (MBS) with 3 wt% ethylene‐butylacrylate‐glycidyl methacrylate tercopolymer (PTW) causes a remarkable increase in toughness of the PC/PBT/RDP blend while maintaining a high rigidity. A detailed investigation of the flame‐retardant action of PC/PBT/RDP and PC/PBT/RDP/PPO blends was performed using thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), TGA‐FTIR, temperature‐programmed pyrolysis/gas chromatography/mass spectrometry (TPPy/GC/MS), and scanning electron microscopy/energy dispersive spectrometer (SEM/EDS). The results demonstrate that RDP induces a higher char yield at ca. 450 °C and synchronously increases the thermal stability of the blend with PPO. The flame‐retardant role of RDP in the condensed phase was discerned from TGA, FTIR, and SEM/EDS of the residues. Copyright © 2010 John Wiley & Sons, Ltd.     

Phosphorus polyester versus aluminium phosphinate in poly(butylene terephthalate) (PBT): Flame retardancy performance and mechanisms

Pyrolysis and fire behaviour of a phosphorus polyester (PET-P-DOPO) have been investigated. The glycol ether of the hydroquinone derivative of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was used as a reactive halogen-free flame retardant in PET-P-DOPO. PET-P-DOPO is proposed as an alternative to poly(butylene terephthalate) (PBT) with established halogen-free additives. It exhibits a high LOI (39.3%) and achieves V-0 classification in the UL 94 test. Three different mechanisms (flame inhibition, charring and a protection effect by the intumescent char) contribute to the flame retardancy in PET-P-DOPO and were quantified with respect to different fire risks. The fire load was reduced by 66% of the PBT characteristic. The reduction is the superposition of the relative reduction due to flame inhibition (factor 0.625) and charring (factor 0.545). The peak of heat release rate (pHRR) was reduced by 83% due to flame inhibition, charring and the protection properties of the char (factor 0.486). The strength of all three mechanisms is in the same order of magnitude. The intumescent multicellular structure enables the char to act as an efficient protection layer. PBT flame-retarded with aluminium diethylphosphinate was used as a benchmark to assess the performance of PET-P-DOPO absolutely, as well as versus the phosphorus content. PET-P-DOPO exhibits superior fire retardancy, in particular due to the additional prolongation of the time to ignition and increase in char yield. PET-P-DOPO is a promising alternative material for creating halogen-free flame-retarded polyesters.     

Flame retardancy mechanisms of poly(1,4‐butylene terephthalate) containing microencapsulated ammonium polyphosphate and melamine cyanurate

The flame retardancy mechanisms of poly(1,4‐butylene terephthalate) (PBT) containing microencapsulated ammonium polyphosphate (MAPP) and melamine cyanurate (MC) were investigated via pyrolysis analysis (thermogravimetric analysis (TGA), real‐time Fourier transform infrared (FTIR), TG‐IR), cone calorimeter test, combustion tests (limited oxygen index (LOI), UL‐94), and residue analysis (scanning electron microscopy (SEM)). A loading of 20 wt% MC to PBT gave the PBT composites an LOI of 26%, V‐2 classification in UL‐94 test and a high peak heat release rate (HRR) in cone calorimeter test. Adding APP to PBT/MC composites did not improve their flame retardancy. In comparison with the addition of ammonium polyphosphate (APP) to PBT, MAPP with silica gel shell and MAPP with polyurethane shell both promoted the intumescent char‐forming and improved the flame retardancy of PBT through different mechanisms in the presence of MC. These two halogen‐free PBT composites with V‐0 classification according to UL‐94 test were obtained; their LOI were 32 and 33%, respectively. Copyright © 2010 John Wiley & Sons, Ltd.     

Mussel‐inspired decoration of Ni(OH)2 nanosheets on 2D MoS2 towards enhancing thermal and flame retardancy properties of poly(lactic acid)

In the present work, a facile and environmental method was developed to fabricate the novel functionalized MoS₂ hybrid. Firstly, MoS₂ nanosheets were coated with polydopamine (PDA) through the self‐polymerization of dopamine (MoS₂‐PDA) in a buffer solution. Then the decoration of Ni(OH)₂ on the MoS₂‐PDA was synthesized because of the strong affinity of Ni²⁺ with hydroxyl groups in PDA. Finally, the as‐synthesized MoS₂‐PDA@Ni(OH)₂ was introduced into poly(lactic acid) (PLA) matrix to explore flame retardancy, thermal stability, and crystalline property of the composites. As confirmed by X‐ray diffraction (XRD), Fourier‐transform infrared spectrometer (FTIR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA), the MoS₂ nanosheets were dually modified with PDA and Ni(OH)₂ without destroying the original structures. The thermal degradation of PLA with MoS₂‐PDA@Ni(OH)₂ generated a notably higher yield of char. Moreover, the crystallization rate of composites is higher than neat PLA. The cone calorimeter test revealed that the introduction of 3% MoS₂‐PDA@Ni(OH)₂ resulted in lower Peak Heat Release Rate (PHRR) (decreased by 21.7%). Thus, the research provided an innovative functionalization method for manufacturing PLA composites with high performances.     

Effect of silica nanoparticles on solid state polymerization of poly(ethylene terephthalate)

In the present study, the effect of silica nanoparticles, on the solid state polycondensation (SSP) kinetics of poly(ethylene terephthalate) (PET) is thoroughly investigated. At silica concentrations less than 1 wt% and reaction temperatures between 200 and 230 °C higher intrinsic viscosity (IV) values were measured, compared to neat PET at all reaction times. However, with 1 wt% of nanosilica (n-SiO₂), the IV increase of the nanocomposites was similar to that of neat PET and a further increase to 5 wt% n-SiO₂ resulted in significantly lower IV values. A simple kinetic model was also employed to predict the time evolution of IV, as well as the carboxyl and hydroxyl content during SSP. The kinetic parameters of the transesterification and esterification reactions were estimated at different temperatures with or without the addition of n-SiO₂. The activation energies of both reactions were determined together with the concentration of inactive end-groups. From the experimental measurements and the theoretical simulation results it was proved that n-SiO₂ in small amounts (less than 1 wt%) enhances both the esterification and transesterification reactions at all studied temperatures acting as a co-catalyst. However, as the amount of nanosilica increases a number of inactive hydroxyl groups were estimated corresponding to participation of these groups in side reactions with the nanosilica particles. These side reactions lead initially to branched PET chains and eventually (5 wt% n-SiO₂ concentration) to crosslinked structures.     

In situ synthesis of a novel transparent poly (methyl methacrylate) resin with markedly enhanced flame retardancy

A novel phosphorus‐containing monomer, (6‐oxido‐6H‐dibenzo[c,e][1,2]oxaphosphinin‐6‐yl)methyl acrylate (DOPO‐AA), is first synthesized and characterized by Fourier transform infrared spectra (FTIR), ¹H nuclear magnetic resonance (NMR) and ³¹P NMR. The monomer is then introduced into poly (methyl methacrylate) (PMMA) matrix via in situ copolymerization to produce a new PMMA based copolymer (PMMA/DOPO‐AA). From UV–vis spectra, microscale combustion calorimeter (MCC) and thermogravimetric analyses (TGA) results, the as‐fabricated PMMA/DOPO‐AA copolymers not only keep relatively high transparency, but also exhibit remarkable improvements in the flame retardancy and thermal stability, such as increased T_0.5 by 60.2°C and limited oxygen index (LOI) by 4.1, and decreased peak heat released rate (PHRR) by 34.7%. Thermal degradation behaviors investigated by real time Fourier transform infrared spectra (RTIR), char structure analysis studied by scanning electron microscope (SEM) and pyrolysis gaseous products studied by TGA coupled with FTIR (TGA‐FTIR) demonstrate that the catalytic charring function of DOPO‐AA in condensed phase and DOPO flame retardant systems in the gas phase are two key factors for the property enhancements. This work not only provides a promising flame‐retardant monomer for polymers, but also will stimulate more efforts on the development of DOPO‐containing flame‐retardant monomers. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of activated carbon black nanoparticles on solid state polymerization of poly(ethylene terephthalate)

Solid state polycondensation (SSP) is a conventional method used to increase the molecular weight of poly(ethylene terephthalate) (PET) in order to become more suitable for applications as carbonated soft drink bottles, etc. In the present study, the effect of activated carbon black (ACB) nanoparticles, on the SSP kinetics is examined. TEM micrographs revealed that ACB was finely dispersed into PET matrix as individual nanoparticles without creating agglomerates. Intrinsic viscosity (IV) measurements revealed that at temperatures 210 and 220 °C the activated carbon black does not influence the IV increase. However, at 230 and 240 °C an accelerating effect was found and higher intrinsic viscosity values were measured, compared to neat PET. Furthermore, a simple kinetic model was employed to predict the time evolution of IV, as well as the carboxyl and hydroxyl content during SSP. The kinetic parameters of the transesterification and esterification reactions were estimated at different temperatures with or without the addition of ACB. From the experimental measurements and the theoretical simulation results it was proved that ACB enhances the esterification reaction at all studied temperatures acting as a co-catalyst. However, the transesterification reaction remains unaffected by the presence of ACB at elevated temperatures (230 or 240 °C), while it is reduced at lower values (210 and 220 °C). Finally, the activation energies of both transesterification and esterification were determined together with the concentration of inactive end-groups.     

The incorporation of rigid diol monomers into poly(butylene terephthalate) via solid‐state copolymerization and melt copolymerization

Incorporation of 2,2‐bis[4‐(2‐hydroxyethoxy)phenyl]propane (Dianol 220®) into poly(butylene terephthalate) (PBT) via solid‐state copolymerization (SSP) showed that Dianol, besides being the reactant, also acts as a swelling agent for rigid amorphous PBT chain segments. Being swollen, these amorphous chain segments become sufficiently mobile to contribute to the SSP process. The thermal behavior of the resulting copolyesters is comparable with melt copolymerized copolymers, although having a different chemical microstructure. The main reason is a full miscibility in the melt of unmodified PBT chain segments and modified chain segments, which eliminates the advantages of a blocky microstructure for the SSP copolyesters. However, incorporation of 2,2′‐biphenyldimethanol (BDM) into PBT resulted in a higher crystallization temperature compared with PBT–Dianol copolymers of equal composition. Preordering of polymer chains in the melt by incorporating rigid, phase separating BDM‐moieties, preferably via SSP to obtain a non‐random distribution, may be the origin of the enhanced crystallization temperature. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1203–1217, 2008     

An investigation into synergistic effects of rare earth oxides on intumescent flame retardancy of polypropylene/poly (octylene‐co‐ethylene) blends

Synergistic effects of two kinds of rare earth oxides (REOs), neodymium oxide (Nd₂O₃) or lanthanum oxide (La₂O₃) on the intumescent flame retardancy of thermoplastic polyolefin (TPO) made by polypropylene/poly (octylene‐co‐ethylene) blends were investigated systemically by various methods. The limiting oxygen index (LOI) of flame retardant TPO (FRTPO) filled by 30 wt% intumescent flame retardants (IFR) composed of ammonium polyphosphate (APP) and pentaerythritol (PER) has been increased from 30 to 32.5 and 33.5 when 0.5 wt% of IFR was substituted by La₂O₃ and Nd₂O₃, respectively. Cone calorimetry tests also reveal the existence of synergistic effects. Thermalgravimetric analyses (TGA) demonstrate that the presence of REOs promotes the esterification and carbonization process in low‐temperature range while enhances the thermal stability of IFR and FRTPO in high‐temperature range. X‐ray diffraction (XRD) reveals that the interaction of Nd₂O₃ with IFR results in the formation of neodymium phosphate (NdP₅O₁₄) with high‐thermal stability. Thermal scanning rheological tests show that the presence of REOs increases complex viscosity of FRTPO in the temperature range of 190～300°C so as to suppress melt dripping but decreases the complex viscosity and increases the loss factors tan δ in temperature range of 300～400°C to make the carbonaceous strucuture more flexible and viscous to resist stress, expand better and keep intact. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis of poly(l-lactic acid) with improved thermal stability by sulfonic acid-catalyzed melt/solid polycondensation

Melt/solid polycondensation (MP/SSP) is deemed as an alternative synthetic route besides ring-opening polymerization (ROP) in synthesizing poly(l-lactic acid) (PLLA). However, it is found that PLLA synthesized by MP/SSP has much poorer thermal stability than that by ROP due to more residual Sn(II) metallic catalyst in the former, but sulfonic acids does not show any detrimental effect on the thermal stability of PLLA. To synthesizing PLLA with good thermal stability by MP/SSP, a variety of commercially available sulfonic acids were screened as catalysts in MP/SSP of PLLA. Among these nonmetallic catalysts, it was found that 1,3-propanedisulfonic acid (PSA) and 1,5-naphthalene disulfonic acid (NSA) exhibited satisfactory catalytic reactivity and PLLAs with excellent thermal stability, high molecular weight, little coloration and good optical purity were successfully synthesized by MP/SSP. The decomposition temperature was increased by 80–100 °C in comparison to SnCl₂-catalyzed PLLA, and the thermal stability is comparable to commercial PLLA produced by ROP.     

Partially renewable copolyesters prepared from acetalized d‐glucitol by solid‐state modification of poly(butylene terephthalate)

The backbone of poly(butylene terephthalate) (PBT) was modified with 2,4:3,5‐di‐O‐methylene‐D ‐glucitol (Glux) using solid‐state modification (SSM). The obtained copolyesters proved to have a non‐random overall chemical microstructure. The thermal properties of these semicrystalline, block‐like, Glux‐based materials were extraordinary, showing higher melting points, and glass transition temperatures compared with other sugar‐based copolyesters prepared by SSM. These remarkable thermal properties were a direct result of the inherently rigid structure of Glux and the relatively slow randomization of the block‐like chemical microstructure of the Glux‐based copolyesters in the melt. SSM proved to be a versatile tool for preparing partially biobased copolyesters with superior thermal properties. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 164–177     

The use of melt rheology and solution viscometry for degradation study of post-consumer poly(ethylene terephthalate): The effects of the contaminants,reprocessing and solid state polymerization

Rheological measurements and intrinsic viscosity were performed to determine how the presence of contaminants, reprocessing and solid state polymerization (SSP) affects the degradation of post-consumer poly(ethylene terephthalate) (PET). First, post-industrial PET resin was contaminated with a series of surrogates according to a US-FDA protocol to simulate the worst-case scenario of misuse of PET packaging. The samples were submitted to recycling and SSP process in the presence of surrogates. The rheological data demonstrated that contaminated samples present degradation, even without any additional process. However, when the contaminated samples are submitted to melt extrusion the level of degradation increases. For the SSP process it was found that the surrogates do not interfere in the degradation process. In addition, an empirical analysis was derived based on the existing relationship. This analysis allowed the use of complex viscosity in higher frequencies, that is, out of the Newtonian plateau, and it shows to be as efficient as the zero-shear rate viscosity, allowing to associate the molar mass index of different samples. The data were corroborated from those obtained by the viscometric molar mass index, highlighting the importance of this new method to quantify the degradation in the polymer system.     

Thermal degradation of elastomeric vulcanized poly(ethylene-co-vinyl acetate) (EVM): Chemical and kinetic investigations

The thermal degradation of vulcanized elastomeric poly(ethylene-co-vinyl acetate) (EVM) in inert and oxidative conditions was investigated. Based on the characterization of both condensed and gas phases during the thermal degradation it was possible to propose a reaction scheme of the EVM degradation. In addition, the determination of the kinetic parameters completed the chemical investigations. The thermo-oxidation of vulcanized EVM occurs in five steps, including the cleavage of some cross-linking bonds, the catalytic deacetylation forming polyenes and a charring step, followed by the decomposition and oxidation of the char. It appeared that the curing, and thus the cross-linking nodes, enhances the thermal stability of EVM by favouring the charring. On the other hand the pyrolysis of the polymer is quite not influenced by the vulcanization.     

A study of the conformational stability of poly(β-benzyl l-aspartate), poly(γ-benzyl l-glutamate) and poly(β-benzyl l-aspartate)/poly(γ-benzyl l-glutamate) blend in the solid state by variable-temperature C CP/MAS NMR

¹³C CP/MAS NMR experiments on polypeptides, poly(β-benzyl l-aspartate) (PBLA), poly(γ-benzyl l-glutamate) (PBLG) and PBLA/PBLG blend have been carried out, in order to elucidate the conformational stability of the polypeptides in the solid state over a wide range of temperatures and its blending effect. The PBLA/PBLG blend with a mixture ratio of 1/1 is prepared by adding trifluoroacetic acid (TFA) solution to alkaline water (TFA-alkaline treatment). From these experimental results, it is found that the conformation of PBLA in the PBLA/PBLG blend sample is changed from left-handed helix (α_L-helix and/or ω_L-helix) form to the α_R-helix form, and then the origin of the formation of the α_R-helix form in PBLA comes from the existence of PBLG. Further, from the variable-temperature ¹³C CP/MAS NMR experiments results, it is shown that the conformational behavior of PBLA in the PBLA/PBLG blend is similar to that of the TFA-alkaline treated PBLA, and also the conformational behavior of PBLG in the PBLA/PBLG blend is similar to that of the TFA-alkaline treated PBLG.     

Novel ethero atoms containing polyesters based on 2,6‐naphthalendicarboxylic acid: A comparative study with poly(butylene naphthalate)

Poly(butylene naphthalate) (PBN), poly(diethylene naphthalate) (PDEN), and poly(thiodiethylene naphthalate) (PTDEN) were synthesized and characterized in terms of chemical structure and molecular weight. The polyesters were examined by TGA, DSC, and DMTA. All the polymers showed a good thermal stability, even though depending on chemical structure. At room temperature they appeared as semicrystalline materials; the effect of the introduction along the PBN polymer chain of ether oxygen atoms or sulfur ones was a lowering in the T_g value, a decrement of T_m, and a decrease of the crystallization rate. Changing in chemical structure also affects the main α absorption associated with the glass transition which moves to lower temperature and whose energetic requirements decrease. The results were explained as due to the presence of highly flexible C? S? C or C? O? C bonds in the polymeric chain. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1694–1703, 2007     

Thermochromism in nickel(II) complexes: thermal, solid state H NMR and single crystal X-ray analysis of bis-(N,N-dimethyl-1,2-ethanediamine) nickel(II) perchlorate

The complex bis-(N,N-dimethyl-1,2-ethanediamine) nickel(II) perchlorate undergoes a first-order thermochromic phase transition at ca. 476 K, changing its color from orange to red. The room temperature X-ray crystal structure determination showed that the nickel ion possesses a square-planar geometry with two five membered chelate rings, in the δλ conformation, forming the NiN₄ chromophore. The broad-line ¹H NMR indicates the onset of a dynamic disorder of diamine chelate rings at the phase transition temperature region, while T₁ measurement of ¹H affords the activation energy of the puckering metal chelate rings to be 26 kJ mol⁻¹. The electronic spectrum revealed that a weakening of ligand field around the nickel is associated with the phase transition.