Fire retardant halogens

Larsen, E. R. Fire retardants (halogenated). In Kirk-Othmer Encyclopedia of Chemical Technology (3rd edition), Vol. 10, 1980, 373-395. 

Zanetti, M. Camino, G. Canavese, D. Morgan, A.B. Lamelas, F.J. Wilkie, C.A. Fire retardant halogen-antimony-clay synergism in polypropylene layered silicate nanocomposites. Chem. Mater. 2002, 14, 189-193. 

A medium reactive, low viscosity, UV stabilised, transparent, fire retardant halogenated resin. Fire properties can be enhanced by the addition of antimony trioxide, b. 63% c. 420 - 610... 

Another factor potentially affecting the market for halogenated fire retardants is the waste disposal of plastics (see Wastes, industrial). As landfiU availabihty declines or becomes less popular, two alternatives are incineration and recycling (qv). The nature of the combustion products from halogenated products requires carefiil constmction and maintenance of incinerators (qv) to avoid damage to the incinerator itself and a pubHc health problem from the exhaust. The ease of recycling used products also has a potential effect on fire retardants. 

Cables are available in a variety of constmctions and materials, in order to meet the requirements of industry specifications and the physical environment. For indoor usage, such as for Local Area Networks (LAN), the codes require that the cables should pass very strict fire and smoke release specifications. In these cases, highly dame retardant and low smoke materials are used, based on halogenated polymers such as duorinated ethylene—propylene polymers (like PTFE or FEP) or poly(vinyl chloride) (PVC). Eor outdoor usage, where fire retardancy is not an issue, polyethylene can be used at a lower cost. 

Phosphate Esters. The principal advantage of phosphate esters is the improved fire retardancy relative to phthalates. The fire performance of PVC itself, relative to other polymeric materials, is very good due to its high halogen content, but the addition of plasticizers reduces this. Consequendy there is a need, in certain demanding appHcations, to improve the fire-retardant behavior of dexible PVC. 

Fire retardant, has low smoke and low halogen emission under fire conditions... 

The role of antimony oxide is not entirely understood. On its own it is a rather weak fire retardant although it appears to function by all of the mechanisms listed above. It is, however, synergistic with phosphorus and halogen compounds and consequently widely used. Other oxides are sometimes used as alternatives or partial replacements for antimony oxide. These include titanium dioxide, zinc oxide and molybdenic oxide. Zinc borate has also been used. 

The self-extinguishing characteristics of the chlorine-containing resins are improved by incorporation of antimony oxide but this approach is not possible where translucent sheet is required. As an alternative to chlorine-based systems a number of bromine-containing resins have been prepared and, whilst claimed to be more effective, are not currently widely used. It is probably true to say that fire-retarding additives are used more commonly than polymers containing halogen groupings. 

While melamine is widely used in flexible foams as a fire-retardant, trichlorphenyl phosphate has been the preferred agent for use in rigid foams. However, the introduction of specifications stipulating halogen-free additives has led to a search for alternatives such as halogen-free phosphorus esters, red phosphorus and ammonium polyphosphate. 

Whilst rigid closed-cell polyurethanes are excellent thermal insulators they do suffer from a limited and often unsatisfactory level of fire resistance, even in the presence of phosphorus-containing and halogen-containing fire retardants. Considerable promise is now being shown by the polyisocyanurates, which are also based on isocyanate chemistry. 

Antimony trioxide (SbaOj). It is produced from stibnite (antimony sulphide). Some typical properties are density 5.2-5.67 g/cm- pH of water suspension 2-6.5 particle size 0.2-3 p,m specific surface area 2-13 m-/g. Antimony trioxide has been the oxide universally employed as flame retardant, but recently antimony pentoxide (SbaOs) has also been used. Antimony oxides require the presence of a halogen compound to exert their fire-retardant effect. The flame-retarding action is produced in the vapour phase above the burning surface. The halogen and the antimony oxide in a vapour phase (above 315 C) react to form halides and oxyhalides which act as extinguishing moieties. Combination with zinc borate, zinc stannate and ammonium octamolybdate enhances the flame-retarding properties of antimony trioxide. 

Zinc in contact with wood Zinc is not generally affected by contact with seasoned wood, but oak and, more particularly, western red cedar can prove corrosive, and waters from these timbers should not drain onto zinc surfaces. Exudations from knots in unseasoned soft woods can also affect zinc while the timber is drying out. Care should be exercised when using zinc or galvanised steel in contact with preservative or fire-retardant-treated timber. Solvent-based preservatives are normally not corrosive to zinc but water-based preservatives, such as salt formulated copper-chrome-arsenic (CCA), can accelerate the rate of corrosion of zinc under moist conditions. Such preservatives are formulated from copper sulphate and sodium dichromate and when the copper chromium and arsenic are absorbed into the timber sodium sulphate remains free and under moist conditions provides an electrolyte for corrosion of the zinc. Flame retardants are frequently based on halogens which are hygroscopic and can be aggressive to zinc (see also Section 18.10). 

Antimony trioxide and chlorinated paraffinic derivatives are common materials used as fire retardants, as are intumescent zinc (or calcium) borate, aluminium hydroxide and magnesium hydroxide. These inorganic materials, used as bulk fillers, act to reduce the fire hazard. Halogenated materials release chlorine, which then combines with the antimony trioxide to form the trichloride, which is a flame suppressant. 

The carbon black generated by a fire from a rubber source increases the smoke density other products are highly toxic and often corrosive. The halogens, phosphates, borates, and their acids evolved during a fire corrode metals and electrical and electronic equipment. Hence many of the fire retardants described below cannot be used in situations where the toxic gases evolved will create their own hazards. In these cases inorganic hydroxides are used, at filler-type addition levels. Aluminium hydroxide and magnesium hydroxide are used as non-toxic fire retardant systems. 

The first fire retardant polyester containing a reactive fire retardant monomer was introduced by the Hooker Electrochemical Corporation in the early 1950 s containing chlorendic acid as the reactive monomer (6). This pioneering development rapidly led to the introduction of variety of reactive halogen and phosphorus containing monomers, such as tetrabromophthalic anhydride, chlorostyrene and tetrabromobisphenol A, which found application in a wide variety of condensation polymer systems. 

FIRE RETARDANT FILLERS. The next major fire retardant development resulted from the need for an acceptable fire retardant system for such new thermoplastics as polyethylene, polypropylene and nylon. The plasticizer approach of CP or the use of a reactive monomer were not applicable to these polymers because the crystallinity upon which their desirable properties were dependent were reduced or destroyed in the process of adding the fire retardant. Additionally, most halogen additives, such as CP, were thermally unstable at the high molding temperatures required. The introduction of inert fire retardant fillers in 1965 defined two novel approaches to fire retardant polymers. 

The third composition in Table IV seems to be related to the aromatic sulfonate/polycarbonate technology just discussed with some modifications being necessary in order to compensate for the aliphatic nature of the polypropylene (17. 181 substrate. In this case the aromatic sulfonate is replaced with a metal salt (preferably magnesium stearate). A silicone oil and or gum has been added to enhance the intumescent character and a small amount of inert filler and decabromodiphenyl oxide is included probably to improve the molding characteristics of the total composition. Fire retardant compositions with a good surface char can be obtained at total loadings only about half that required for the halogen/antimony oxide composition. 

J.J. Pitts, "Antimony-Halogen Synergistic Reactions in Fire Retardants, "J. Fire Flamm., 51 (1972). 

S.K. Brauman and A.S. Brolly, "Sb203 - Halogen Fire Retardance in Polymers I. General Mode of Action,"... 

Chamberlain, "Sb203-Halogen Fire Retardance in Polymers IV. Combustion Performance, "Journal of Fire Retardant Chemistry, 2, 225 (1976). 

The purpose of this paper is to briefly review recent research into the effectiveness and mode of action of tin compounds as fire retardants in a number of halogenated and halogen-free, plastic and elastomeric substrates. 

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