New generation of fire retardant polyester resins

Smoke evolution [in a smoke chamber (750 x 750 x 1000) ± 5 mm, Polish Standard PN-91/K-02501 equivalent to UIC 561-OR (1991)] was studied in, and the oxygen index flammability test (Polish Standard PN-76/C-89020) was carried out for, glass-reinforced polyester (GRP) laminates obtained with unsaturated polyester (UP) resins containing chlorine and bromine in the chain. In these studies, the effect on these properties of such additives as ZnSnO₃ (ZS), ZnSn(OH)₆ (ZHS), Al(OH)₃ or Mg(OH)₂ and Sb₂O₃ in an amount of up to 30 mass-% was determined. The most efficient ignition and smoke-evolution retarder from among the investigated compounds was ZS and ZHS, whereas an essential reduction in smoke evolution was observed also with Sb₂O₃. GRP laminates with these additives meet the fire-safety recommendations concerning smoke evolution from materials used in transportation means and in the building industry.     

Synthesis and fire retardant properties of vinylic polymers bearing phosphonated groups

To overcome the use of halogenated compounds, which are usually incorporated in plastics as flame retardant additives, the authors investigated the synthesis possibilities, to introduce with covalent bonds, the flame retarder groups at different positions of the polymer chains. They established correlations between the topology of the phosphonated groups and the flame retardant properties. They attempt to determine the origin of the flame resistance obtained in several cases. Their goal is to extend their interesting results obtained from oligomers, to polymer of high molecular weight.     

Catalytic fire retardant nanocomposites

In this paper the chemical activity of carbon nanotubes and polyhedral oligomeric silsesquioxane during thermal degradation and combustion of polymer nanocomposites is addressed. Indeed, polymer-nanofiller systems may exhibit chemical effects capable of thermal stabilisation of polymers as well as reduction of combustion rate and heat released, owing to catalytic effects induced by the nanofillers at high temperature.Carbon nanotubes in the presence of oxygen are shown to promote oxidative dehydrogenation in polyethylene with production of a stable surface layer of carbon char that provides an effective oxygen barrier effect. A similar action is performed by metal-containing polysilsesquioxanes dispersed in polypropylene.With either carbon nanotubes or metal POSS, partial carbonisation of the polymer matrix occurs during combustion, subtracting part of the organic polymer from combustion, targeting one of the major fire retardancy aim.     

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.     

The application of hydrated mineral fillers as fire retardant and smoke suppressing additives for polymers

The characteristics of hydrated mineral fillers are discussed with reference to their use as fire retardant additives for polymers. Particular consideration is given to their mode of action and criteria which influence their performance, both in reducing polymer flammability and in suppressing smoke evolution during combustion. Methods for reducing their adverse effect on mechanical properties of the host polymer are also highlighted.     

Diglycidylphenylphosphate based fire retardant liquid crystalline thermosets

Organophosphorus liquid crystalline thermosets (LCTs) were developed using diglycidylphenylphosphate (DGPP) and various aromatic diamines. DGPP was prepared by the esterification of phenylphosphorodichloridate with glycidol. 2,5-Bis(p-aminophenyl)-1,3,4-oxadiazole (BPOD) was synthesized and three different commercial diamines, 4,4′-diaminodiphenyl sulphone (DDS), 4,4′-diaminodiphenyl methane (DDM) and biphenyl diamine (BPD) were used as curing agents. The mesomorphic behaviour of DGPP/diamine mixtures and their curing kinetics were monitored by differential scanning calorimetry and hot stage optical polarized microscopy. The thermogravimetric analysis data showed that the LCTs are stable in the range 261-292 °C and afford 36-48% char yield. The limiting oxygen index values are between 35 and 47 proving fire retardance. The mechanical properties of the cured LCTs were characterized by dynamic mechanical analysis.     

阻燃剂FR-421的研制

研究开发阻燃性能优越、与合成材料相容性好、低毒无烟、耐久的阻燃剂是当务之急。磷酸酯齐聚物是近十几年来出现的一种高分子聚合物阻燃剂 ,与小分子阻燃剂相比 ,具有分子量高、蒸汽压低、迁移性小、耐久性好、毒性低、多功能等特点 ,可用于ＰＥ、ＡＢＳ、ＰＥＴ、ＳＡＮ、ＰＰ等合成材料的阻燃[1 - 3] 。本文以四溴双酚 -Ａ、2 ,3-二溴丙醇、三氯氧磷为主要原料 ,按下面的路线合成了四溴双酚 -Ａ磷酸酯齐聚物阻燃剂 (以下简称为阻燃剂ＦＲ - 42 1 )。1　实验部分1 .1　药品与仪器四溴双酚 -Ａ和三氯氧磷 (工业品 ,连云港双菱化工集团公司 …     

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.     

Thermal behaviour of bromine-metal fire retardant systems

Chemical reactions which occur on heating fire retardant mixtures of decabromodiphenyloxide (DBDPO) with antimony trioxide (AO) or bismuth carbonate (BC) have been studied by means of weight loss, elemental analysis, X-ray diffraction, scanning electron microscopy (SEM) and energy dispersive system (EDS) microanalysis.

It has been shown that on rapid heating to 700°C, DBDPO volatilisation competes with debromination by AO or BC leading to volatile SbBr₃ or BiBr₃ which are formed by different mechanisms. BC is rapidly transformed into BiOBr which gives BiBr₃ by further debromination of DBDPO. At high conversion (high temperature) this process is in competition with reduction of BiOBr to metallic bismuth. In the case of AO slower formation of progressively bromine-richer antimony oxybromides takes place which liberates SbBr₃ by thermal degradation.

The formation of a rod-shaped Br-Sb containing phase is shown to relate to the progression of chemical reactions which occur on heating the AO-DBDPO mixture.     

Performance of intumescent fire retardant for wood

Performance characteristics of new fire-retardant formulations are studied, including their water resistance and the effect of additives.     

Coir-fiber-based fire retardant nano filler for epoxy composites

Coir-fiber-based fire retardant nano filler has been developed for epoxy resin (ER). At first, the coir fiber was brominated with saturated bromine water and then treated with stannous chloride solution. After drying, it was grinded to nano dimension and mix well with ER for composites preparations. FTIR, DSC, and TG techniques were used to characterize the brominated coir fiber. Gravimetric analysis shows only 10% by mass of bromination on coir fiber. Bromination decreases the thermal stability of the coir fiber, but it does not affect the final stability of the composites. This study concentrates on the thermal, fire retardant, and morphological properties of nanocomposites prepared by direct mixing. The fire retardancy properties (smoke density and limiting oxygen index) of coir–epoxy nanocomposites have increased significantly.     

Mechanism of action of a fire retardant chloroparaffin

The mechanism by which a typical fire retardant chloroparaffin imparts fire retardant characteristics to high density polyethylene, polypropylene and polystyrene is studied by comparing the oxygen indices of these mixtures measured before and after dehydrochlorination. It is shown that flame poisoning by HCl evolved from the chloroparaffin is negligible in polystyrene and high density polyethylene, whereas it is noticeable in polypropylene. The results obtained are related to previous data on the thermal degradation of these mixtures. It is concluded that the chloroparaffin acts mainly by modifying the mechanism of pyrolysis of these polymers in the burning process. Only in the case of polypropylene is there an appreciable contribution by flame poisoning.     

Study of the mechanism of intumescence in fire retardant polymers: Part I—Thermal degradation of ammonium polyphosphate-pentaerythritol mixtures

Interactions are shown to take place between ammonium polyphosphate and pentaerythritol in thermally degrading mixtures. Up to 500°C, gaseous products are evolved on programmed heating above 200°C in two steps with maximum rate temperatures differing by about 100–150°C. Swelling of the degrading mass seems, however, to be mainly due to gases evolved in the step occurring at the higher temperature. A strong dependence of the degradation process on the experimental conditions is observed.     

The fire retardant behavior of various chlorides on cellulose

TG, DTA, and TMA data on the pyrolysis of α-cellulase powder in air is reported together with the modified pyrolysis behavior of the cellulose impregnated with between 2–3% (w/w) of calcium, potassium, sodium and zinc chlorides. The lower temperature of onset of the pyrolysis (as shown by TG and TMA), the increased peak areas of the DTA exotherms, and the elimination of an initial endotherm present in the pure cellulose, all suggest an increased flammability for the impregnated samples. Other properties of the impregnated celluloses however favor a fire retardancy effect; these are an increase in the temperature of the first exothermic peak on the DTA, a reduction in the maximum rate of mass loss, a reduction in the% mass loss occurring in the first mass loss period, and an increase in the% ash remaining at 800°C. The relative effect of the various chlorides is examined and shown to correlate with other data already published.     

Study of the mechanism of intumescence in fire retardant polymers: Part II—Mechanism of action in polypropylene-ammonium polyphosphate-pentaerythritol mixtures

It is shown that, by the addition of a typical intumescent mixture of ammonium polyphosphate and pentaerythritol to polypropylene, the mechanism of intumescence which develops on heating is not significantly affected by dispersion of the intumescent mixture in the polymer. On the other hand, in these mixtures, polypropylene seems to evolve, by thermal degradation, a smaller amount of flammable products than when it is heated alone. The ammonium polyphosphate-pentaerythritol additive is shown to induce fire retardant characteristics in polypropylene by means of a ‘condensed phase’ mechanism.     

Flame retardant epoxy polymers based on all phosphorus-containing components

A phosphorus-containing epoxy resin, bis(3-t-butyl-4-glycidyloxyphenyl-2,4-di-t-butylphenyl)resorcinol diphosphate, was synthesized and subsequently cured with non-phosphorus containing amines, and/or novel phosphorus-containing aromatic or polyoxyalkylene amines. Chemical structures of these materials were characterized with FTIR, NMR, elemental analysis, and amine titration. The introduction of soft -P-O- linkage, polyoxyalkyene, or hard aromatic group into the backbones of the synthesized phosphorus-containing amines provides epoxy polymers with high phosphorus contents and tailored flexibility. Thermal analysis of differential scanning calorimeter and thermal gravimetric analysis (TGA) reveals that these resulted epoxy polymers possess moderate T_gs and thermal stability. Furthermore, high char yields in TGA analysis and high limited oxygen index values indicate that these phosphorus-containing epoxy polymers possess excellent flame retardant properties.     

Study of the mechanism of intumescence in fire retardant polymers: Part VI—Mechanism of ester formation in ammonium polyphosphate-pentaerythritol mixtures

It is shown that, on heating ammonium polyphosphate-pentaerythritol mixtures, phosphoric ester bonds are formed first by alcoholysis of the polyphosphate chain. Further intramolecular alcoholysis and/or esterification leads to cyclic pentaerythritol phosphate structures inserted in the polyphosphate chains. Evidence is also given of intermolecular dehydration of pentaerythritol in mixtures with a large excess of alcoholic hydroxy groups over phosphorus atoms. The intumescent behaviour of the mixtures is discussed in relation to the final structure of the product of reaction which depends on the composition of the original mixture.     

Study of the mechanism of intumescence in fire retardant polymers: Part III—Effect of urea on the ammonium polyphosphate-pentaerythritol system

Urea, which is commonly used as a ‘blowing’ co-additive in intumescent coatings, is shown to depress intumescence when it is added to ammonium polyphosphate-pentaerythritol mixtures incorporated into the bulk of polypropylene. Concurrently, the fire retardant properties of the intumescent additive are depressed in the presence of urea although, in this case, a smaller amount of flammable hydrocarbons is evolved in the thermal degradation of the polymer.     

The structure-activity relationship of fire retardant phosphorus compounds in wood

Sawdust of Scots Pine sapwood was chemically modified with various alkyl- and phenylchlorophosphorus compounds. The formation of covalent bonds was confirmed with solid state CP-MAS ¹³C NMR.According to thermogravimetric analysis (TGA), all phosphorus compounds decreased the temperature for the maximum rate of pyrolysis (from 350 °C to max. 240 °C) and increased the char formation (from 25% to max. 54%). Variation of the alkyl groups (C2-C8) had no significant effect. Phenylphosphates decrease the temperature of pyrolysis more efficiently than the alkyl analogues, due to higher thermal stability. The order in which the phenylphosphorus compounds affect the pyrolysis of the modified sawdust is consistent with their acidity order: organophosphate > organophosphonate ? organophosphinate.All phosphorus compounds used in this study reduce the equilibrium moisture content (EMC). Whereas the results obtained with the dialkyl phosphates are relatively poor, significant reductions in EMC can be achieved with the phenylphosphorus compounds.