Thermal degradation of a highly chlorinated paraffin used as a fire retardant additive for polymers

The thermal degradation of a highly chlorinated paraffin, (Cl 70% w/w)(CP), used as a fire retardant additive for polymers, has been studied by TG, DTA and TVA. The main volatile degradation product is HCl which is eliminated in two steps. To 60–70% dehydrochlorination an apparent zero order reaction occurs with a detectable rate from 250°C, probably initiated at labile chlorine atoms. The apparent activation energy of the process is 40 kcal/mole. A charred residue containing 35% chlorine is obtained. This residue undergoes nearly complete dehydrochlorination in the range 300–600°C.     

Thermal decomposition of 4,4′-diaminodiphenylsulphone

The thermal decomposition of 4,4′-diaminodiphenylsulphone (DDS) was studied by thermogravimetry, differential scanning calorimetry and thermal volatilisation analysis. Solid residues, high-boiling and gaseous products of degradation were collected at each step of thermal decomposition and analysed by infrared spectroscopy and gas chromatography/mass spectrometry.

On programmed heating at normal pressure, DDS starts to evaporate at 250°C. Thermal decomposition, which probably proceeds through homolytic scission of the S-C bond is simultaneously observed. The resulting sulphonyl radicals provoke polymerisation and cross-linking of the solid residue which undergoes a limited degradation at 350°C with elimination of heteroatoms N and S as volatile moieties. Above 400°C, the residue undergoes a complex charring process leading to an aromatic char typical of carbonised aromatic polymers.     

Effect of chlorinated fire-retardant additives on the thermal degradation of polypropylene

Modifications in the thermal degradation mechanism of polypropylene caused by interactions between the degrading polymer, a chloroparaffin and bismuth carbonate (typical fire retardant additives) are studied.Preliminary TVA and pyrolysis-GLC results show that volatilisation of the polymer occurs at lower temperatures with production of a larger proportion of higher boiling chain fragments in the mixture than in the pure polymer.The products of a strongly exothermal reaction occurring when the two additives are heated together, as shown by DTA and TG, could play an important role in modifying the thermal degradation behaviour of polypropylene in the mixture.     

Characterisation of fire retardant poly(phenylene ether) high impact polystyrene in the UL-94 test

The distribution of the temperature and the morphology of the charred material formed in the combustion of blends of poly(phenylene ether) (PPE) with high impact polystyrene (HIPS), carried out in the UL94 test, were examined. The effect of the fire retardant triphenyl phosphate is shown to be the decrease of time of burning, of temperature of the specimen and of zone involved in combustion, without apparent modification of the char structure. Hypothesis on gas and condensed phase fire retardant mechanisms are discussed.     

Mechanistic aspects of intumescent fire retardant systems

The mechanism of intumescence is studied in mixtures of ammonium polyphosphate (APP) with several polycondensates as a part of a systematic study of intumescent fire retardants. It is shown that APP reacts on heating with the polycondensate to form a precursor of the intumescent char which is obtained on further heating. The introduction of the intumescent system in polypropylene does not modify the structure of the char formed on heating. However, the polymer modifies the foaming behaviour of the system. The thermal decomposition of the char occurs with volatilisation of phosphorus moieties and formation of a relatively thermally stable residue. Effects of the thermal behaviour of the char, on fire retardance, are discussed.     

Mechanisms of fire retardance in glass fibre polymer composites

It is shown that the introduction of glass fibres in the poly(butylene terephthalate) (PBT) matrix, increases its flammability. The mechanism of action of a typical fire retardant for PBT which is a mixture of a brominated organic compound and antimony trioxide, seems to involve both the condensed and the gas phase.     

On second order degree of graphs

Given a vertex v of a graph G the second order degree of v denoted as d 2(v) is defined as the number of vertices at distance 2 from v.In this paper we address the following question:What are the sufficient conditions for a graph to have a vertex v such that d2(v) ≥ d(v),where d(v) denotes the degree of v? Among other results,every graph of minimum degree exactly 2,except four graphs,is shown to have a vertex of second order degree as large as its own degree.Moreover,every K-4-free graph or every maximal planar graph is shown to have a vertex v such that d2(v) ≥ d(v).Other sufficient conditions on graphs for guaranteeing this property are also proved.     

Thermal degradation of poly(2,6-dimethoxycarbonyl-1,6-heptadiene)

The thermal degradation under vacuum of poly(2,6-dimethoxycarbonyl-1,6-heptadiene), a polymer which contains cyclic structural units, has been investigated. The analysis of the degradation products has shown that depolymerisation (depropagation along the polymer chain with formation of diene monomer) occurs extensively, together with other degradation reactions. A mechanism is proposed to account for the degradation products which have been identified.     

RhIAr/AuIAr′ Transmetalation: A Case of Group Exchange Pivoting on the Formation of M−M′ Bonds through Oxidative Insertion

By combining kinetic experiments, theoretical calculations, and microkinetic modeling, we show that Pf/Rf (C₆F₅/C₆Cl₂F₃) exchange between [AuPf(AsPh₃)] and trans‐[RhRf(CO)(AsPh₃)₂] does not occur by typical concerted Pf/Rf transmetalation via electron‐deficient double bridges. Instead, it involves asymmetric oxidative insertion of the Rh^I complex into the (Ph₃As)Au?Pf bond to produce a [(Ph₃As)Au?RhPfRf(CO)(AsPh₃)₂] intermediate, followed by isomerization and reductive elimination of [AuRf(AsPh₃)]. Interesting differences were found between the LAu?Ar asymmetric oxidative insertion and the classical oxidative addition process of H₂ to Vaska complexes.     

Mechanistic study of thermal behavior and combustion performance of epoxy resins: I homopolymerized TGDDM

Tetraglycidyl 4,4′-diaminodiphenylmethane (TGDDM) undergoes homopolymerization on heating. Intramolecular reactions which compete with crosslinking favor the formation of cyclic structures with increasing thermal and fire resistance of the resin, whereas physical mechanical properties tend to decrease. The mechanism of thermal decomposition of TGDDM is studied by thermogravimetry, differential scanning calorimetry and thermal volatilization analysis with characterization of volatiles evolved and residue left. Thermal degradation of poly-(TGDDM) starts at 260°C with elimination of water from secondary alcoholic groups which is a typical pathway for epoxy resin degradation. Resulting unsaturations weaken bonds in the β-position and provoke the first chain breaking at allyl–amine and allyl–either bonds. With increasing temperature, saturated alkyl–ether bonds and alkyl carbon–carbon bonds are broken first, followed by the most stable alkyl–aryl bonds at T>365°C. The combustion performance of TGDDM is discussed on the basis of the thermal degradation behavior.