Flame Retardation Using Halogen Compounds

One of the principal classes of flame retardants used in plastics and textiles is that of phosphorus, phosphorus—nitrogen, and phosphorus—halogen compounds (see also Flame retardants for textiles). Detailed reviews of phosphoms flame retardants have been pubhshed (1—6) (see also Phosphorus compounds). 

Flame Retardants. Bromine compounds make up an important segment of the market for flame retardants used in polymers. Additive flame retardants are added to polymers during processing reactive flame retardants react chemically to become part of the polymer chain itself. In addition to the compounds Hsted in Table 3, a number of proprietary mixtures and phosphoms—bromine-containing flame retardants are also sold (see Elame RETARDANTS, HALOGENATED, FLAAffi RETARDANTS). 

Flame retardants—Whereas halogen-containing Mannich bases arc mainly used as modifiers of macromolccular materials, as mentioned before, phosphorus derivatives arc employed as additives. These products arc obtained from phosphorous acid or phosphites 584 " and from other analogous phosphorus-containing compounds. N-Heterocyclcs, after reaction with melamine and formaldehyde (585), are also used as (lame retardants. -... 

The most common halogen-based flame retardants used in styrenic polymers are listed in Table 29.1 [23]. The majority of these are brominated aromatic compounds used to flame retard HIPS and ABS. As mentioned in Section 4, roughly 10 wt% of bromine is required to pass UL 94 V-0 requirements. Antimony trioxide is also used in combination with these brominated compounds. 

To combine fire resistance with low smoke and gas formation, a low halogen flame retardant is produced, which contains just 25-26% bromine, which is used at loadings of 4-6%. Most of the widely used halogenated compounds contain up to 80% halogen [7]. 

Fire resistant PU are obtained by the addition or by introduction into the PU structure of special compounds, called flame retardants. The flame retardants are organic compounds containing halogens (chlorine, bromine) and phosphorus. Compounds of antimony (Sb) or boron [1-13] are rarely used. Sometimes inorganic compounds are used as flame retardants for PU, such as, hydrated alumina (Al203 nH20), Sb203 or ammonium polyphosphate [1-3, 14]. 

These types of products, both soluble and insoluble, can be produced in a number of ways (186-192) with d rees of oxygen and alkyl group loss increasing with the severity of the reaction conditions. However, there is no current use for these compounds and no production of them. Further, if these materials are to be used as flame retardants, the halogenation that is coincident with phosphorylalion by strong electrophiles will have to be avoided and other, potentially less cost-effective, synthetic routes to these materials must be developed. 

The second area of research is flame-resistant or nonflammable electrolyte solutions. The main approach is to employ phosphate compounds in some way, either by using cyclic phosphoric acid ester as solvent or by adding a phosphazene compound as flame retardant. The next most common approach is to use halogen compounds, especially fluorine compounds such as fluorocarbon ester and fluorinated ether, as solvent. There is also the concept of a new safety mechanism whereby a flame retardant is encased in microcapsules to be released in case of battery malfunction. 

Unsaturated Polyesters. There are two approaches used to provide flame retardancy to unsaturated polyesters. These materials can be made flame resistant by incorporating halogen when made, or by adding some organic halogen compound when cured. In either case a synergist is needed. The second approach involves the addition of a hydrated filler. At least an equal amount of filler is used. 

Reactive Flame Retardants. Reactive flame retardants become a part of the polymer by either becoming a part of the backbone or by grafting onto the backbone. Choice of reactive flame retardant is more complex than choice of an additive type. The reactive flame retardant can exert an enormous effect on the final properties of the polymer. There are also reactive halogenated compounds used as iatermediates to other flame retardants. Tables 8 and 9 Hst the commercially avaHable reactive flame retardants and iatermediates. 

Antagonism between antimony oxide and phosphoms flame retardants has been reported in several polymer systems, and has been explained on the basis of phosphoms interfering with the formation or volatilization of antimony haUdes, perhaps by forming antimony phosphate (12,13). This phenomenon is also not universal, and depends on the relative amounts of antimony and phosphoms. Some useful commercial poly(vinyl chloride) (PVC) formulations have been described for antimony oxide and triaryl phosphates (42). Combinations of antimony oxide, halogen compounds, and phosphates have also been found useful in commercial flexible urethane foams (43). 

Ethylene vinyl acetate (EVA) polymers are used in thermoplastic and thermosetting jacketing compounds for apphcations that require flame retardancy combined with low smoke emission during the fire as well as the absence of halogen in the composition. 

Flame and Smoke Retardants. Molybdenum compounds are used extensively as flame retardants (qv) (93,94) in the formulation of halogenated polymers such as PVC, polyolefins, and other plastics elastomers and fabrics. An incentive for the use of molybdenum oxide and other molybdenum smoke and flame retardants is the elimination of the use of arsenic trioxide. Although hydrated inorganics are often used as flame retardants, and thought to work by releasing water of crystallization, anhydrous molybdenum oxides are effective. Presumably the molybdenum oxides rapidly form... 

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