Vapor-phase flame-retardant mechanisms

Highly efficient and versatile for wide range of applications. Requires uses of antimony oxide. Broad range of high-performance products available, as aromatic, cycloaliphatic, and bromine/chlorine paraffins. Vapor-phase flame-retardant mechanism. Flame-retardant elements interrupt chemical reactions of combustion in flame zone. 

Vapor-Phase Mechanisms. Phosphoms flame retardants can also exert vapor-phase flame-retardant action. Trimethyl phosphate [512-56-1] C H O P, retards the velocity of a methane—oxygen flame with about the same molar efficiency as antimony trichloride (30,31). Both physical and chemical vapor-phase mechanisms have been proposed for the flame-retardant action of certain phosphoms compounds. Physical (endothermic) modes of action have been shown to be of dominant importance in the flame-retardant action of a wide range of non-phosphoms-containing volatile compounds (32). 

To provide flame retardancy to the polymer, there are three main mechanisms that a flame retardant can use, and the most effective flame retardants use two or all three mechanisms in concert. The first is by altering the gas phase or combustion chemistry. Additives that work by this mechanism are referred to as vapor phase flame retardants (see Fig. 1) during combustion. Halogenated and some phosphorus flame... 

Halogenated flame retardants such as chlorinated paraffins, chlorocycloaliphatics, and chloro- and bromoaromatic additives, which are commonly employed in flame-retarding plastics, are postulated to function primarily by a vapor-phase flame-inhibition mechanism. Flame retardation could be implemented by incorporating fire-retardant additives, impregnating the material with a flame-retardant substance, or using flame-retardant comonomers in the polymerization or grafting. 

The question as to whether a flame retardant operates mainly by a condensed-phase mechanism or mainly by a vapor-phase mechanism is especially comphcated in the case of the haloalkyl phosphoms esters. A number of these compounds can volatilize undecomposed or undergo some thermal degradation to release volatile halogenated hydrocarbons (37). The intact compounds or these halogenated hydrocarbons are plausible flame inhibitors. At the same time, thek phosphoms content may remain at least in part as relatively nonvolatile phosphoms acids which are plausible condensed-phase flame retardants (38). There is no evidence for the occasionally postulated formation of phosphoms haUdes. Some evidence has been presented that the endothermic vaporization and heat capacity of the intact chloroalkyl phosphates may be a main part of thek action (39,40). 

Phosphorus promotes char formation to protect substrate, and halogen acts in vapor phase. Good thermal stability. Process with modified PPO up to 550-600°E Flame-retardant mechanism condensed phase. Flame retardant induces reactions in host resin that lead to charring and insulation against further burning. 

Mechanism. Alumina trihydtate functions as a flame retardant in both the condensed and vapor phases (26). When activated, it decomposes endothermically, eliminating water. 

The mechanism by which tin flame retardants function has not been well defined, but evidence indicates tin functions in both the condensed and vapor phases. In formulations in which there is at least a 4-to-l mole ratio of halogen to tin, reactions similar to those of antimony and halogen are assumed to occur. Volatile stannic tetrahaUde may form and enter the flame to function much in the same manner as does antimony trihaUde. 

Alkyl diphenyl phosphate plasticizers can exert flame-retardant action in vinyl plastics by a condensed-phase mechanism, which is probably some sort of phosphoms acid coating on the char. Triaryl phosphates appear to have a vapor-phase action (29). 

Triphenylphosphine oxide [791-28-6], C gH OP, and triphenyl phosphate [115-86-6], C gH O P, as model phosphoms flame retardants were shown by mass spectroscopy to break down in a flame to give small molecular species such as PO, HPO2, and P2 (33—35). The rate-controlling hydrogen atom concentration in the flame was shown spectroscopically to be reduced when these phosphoms species were present, indicating the existence of a vapor-phase mechanism. 

Physical or chemical vapor-phase mechanisms may be reasonably hypothesized in cases where a phosphoms flame retardant is found to be effective in a noncharring polymer, and especially where the flame retardant or phosphoms-containing breakdown products are capable of being vaporized at the temperature of the pyrolyzing surface. In the engineering of thermoplastic Noryl (General Electric), which consists of a blend of a charrable poly(phenylene oxide) and a poorly charrable polystyrene, experimental evidence indicates that effective flame retardants such as triphenyl phosphate act in the vapor phase to suppress the flammabiUty of the polystyrene pyrolysis products (36). 

It is our intention to point out clues, mostly from the literature, some from our own work, which suggest approaches to new flame retardant systems with greatly increased efficiency. Both vapor phase and condensed phase mechanisms will be considered. 

Modified-polyphenylene oxide (or ether) is a blend of high impact polystyrene (PS) and polyphenylene oxide (PPO), plus thermal stabilizers and a triarylphosphate flame retardant. Studies of the mechanism of the flame retardant in modified-polyphenylene oxide have shown some evidence for both solid phase and vapor phase inhibition (4). Indeed, one is always interested to know whether flame retardant action is on the solid or vapor phase. 

Boron Mechanism. Boron functions as a flame retardant in both the condensed and vapor phases. Under flaming conditions boron and halogens form the corresponding trihalide. Because boron (rihalides are effective Lewis acids, they promote cross-linking, minimizing decomposition of the polymer into volatile flammable gases. These trihalides arc also volatile thus they vaporize into the (lame and release halogen which Ihen functions as a Maine inhibitor. 

Condensed-Phase Mechanisms. The mode of action of phosphorus-based flame retardants in cellulnsic sy stems is probably best understood. Cellulose decomposes by a noncalalyzed route lo tarry depolymerization products, notably levoglucosan, which then decomposes to volatile combustible fragments such as alcohols, aldehydes, ketones, and hydrocarbons. However, when catalyzed by acids, the decomposition of cellulose proceeds primarily as an endothermic dehydration of the carbohydrate to water vapor and char. Phosphoric acid is particularly efficaceous in this catalytic role because of its low volatility (see Phosphoric Acids and Phosphales). Also, when strongly heated, phosphoric acid yields polyphosphoric acid which is even more effective in catalyzing the cellulose dehydration reaction. The flame-retardanl action is believed to proceed by way of initial phosphory lation of the cellulose. 

Vapor-Phase Mechanisms. Phosphorus flame retardants can also exert vapor-phase llamc-rctardam acliun. Both physical and chemical vapor-phase mechanisms have been proposed lor the flamc-reuirdatit action of certain phosphorus compounds, such as triphenvl phosphate. 

The mechanism of action of an effective fire retardant acting in the vapor phase should inhibit one or both reactions (Equation 4.2 and Equation 4.3) because they have a paramount effect on the increase of the overall rate of thermal oxidation process occurring in the flame. Indeed, the reaction represented by Equation 4.2 increases radical concentration while reaction represented by Equation 4.3 increases the temperature. From a mass spectrometry study of species sampled in low-pressure flame,4 it is evident that the introduction of halogen species into a premixed CH4/02 flame leads to the production of the hydrogen halide, HX, early in the flame. It was also observed that the production of H2 is enhanced. This provides evidence for removal of H atoms from the flame and the predominant reaction is considered to be... 

It has been reported that the effectiveness of copolymerized DOPO-type monomers can be further improved if the alcohol-amine derivatives of DOPO, for example, Structure 5.11, are used rather than similar structures not containing nitrogen.30 Of the FR fibers based on P-containing comonomers, it has been found that those based on Structure 5.10 are more hydrolytically stable, presumably because the P-containing group is in a cyclic structure and also should the hydrolysis of the P-0 bond occur, it will not lead automatically to a marked reduction in molecular weight.31 All the P-modified PETs appear to be subject to both the vapor-and condensed-phase mechanisms of flame retardance, with the former predominating.32 33... 

A predominantly vapor-phase mechanism of flame retardation has been proposed for flame retardants based on triphenylphosphine oxide and triphenyl phosphate has been proposed (Scheme 5.1). 

As mentioned previously, when polystyrene is subjected to the temperatures of a flame it pyrolyzes by a depolymerization mechanism to give monomer and oligomers [14]. The combustion of these volatile products in the vapor phase above the sample supplies heat back to the solid sample (Figure 29.3). If the energy supplied by combustion is sufficient to maintain the pyrolysis process, the flame is self-sustaining even after the test flame has been removed. In order to make polystyrene more flame retardant, the cycle of pyrolysis and combustion must be broken. Flame retardants may act in either the vapor or solid (condensed) phase. 

Although much work has been carried out on the mode of action of flame retardants generally, the mechanisms associated with tin additives are only partially understood. It is clear that tin-based fire retardants can exert their action in both the condensed and vapor phases, and that the precise action in any particular system depends on a number of factors, including incorporation level, the amount and chemical nature of other additives present, and the nature of the polymer itself. 

Many theories attempt to explain the mechanism of flame retardancy. The flame retarding action is thought to take place in the vapor phase above the burning surface. For antimony oxide to work, the halogen and antimony oxide must be found in a vapor phase which will occur at temperatures above 315°C. At these temperatures, antimony halides and oxyhalides are formed and act as flame extinguishing moieties by quenching radicals as they form. 

Prins et al. (21) described the lower flammability of poly-bromostyrene relative to that of polystyrene. On the basis of thermal analysis experiments, they suggested that bromine inhibited most of the oxidative chain reactions, and thus the combustion was not supported (vapor-phase mechanism). Khanna and Pearce (16) and Brauman (22) demonstrated that polystyrene could be flame retarded by appropriately modifying its structure with substituents that promote the char yield of the system (condensed-phased mechanism). 

As in polyester resins, reactive halogens containing fire-retardant chemicals are most often used in epoxy materials. Tetrabromobisphenol A is perhaps the most widely used component for flame-retarding epoxy resins. Nara and Matsuyama (24) and Nara et al. (25) described the thermal degradation and flame retardance of tetrabrominated bisphenol A diglycidyl ether compared to the nonbrorainated structure. Their results indicate that bromine acts by vapor-phase as well as condensed-phase mechanisms of flame inhibition. 

The mechanism of burning for polymers is believed to take place through thermal pyrolysis of the solid plastic to produce gases that act as fuel for the fire (45). Fire retardants work in both the condensed and the vapor phase to interrupt melting of the polymer and burning of the gases. Triaryl phosphates function well in the vapor phase. Alkyl aryl phosphates are believed to decompose in the flame front to form polyphosphoric acid, which stays in the condensed phase to form char, which reduces flammability and smoke evolution (46. 47). 

These studies clearly showed that the chemical structure of the phosphorus atom plays a major role in the flame retardancy, with phosphonate groups proving to be more active than the corresponding phosphate groups. Furthermore, phosphonated groups linked to the polymer backbone and obtained by copolymerization had a low effect on mechanical and physical properties in comparison with phosphonated compounds added to polystyrene (PS), where a decrease of these properties was obtained. The additives acted in the vapor phase, whereas phosphonated copolymers were active both in the vapor and condensed phases. 

---