Formulation flame retardants

Some inorganic fillers are used as flame retardants in rubber base formulations. Flame retardants act in two ways (1) limiting or reducing access of oxygen to the combustion zone (2) reacting with free radicals (especially HO ), thus acting as terminator for combustion-propagation reaction. The additives most widely used as flame retardants for polymers are antimony oxides and alumina trihydrate. 

The benchmark achieved by each of the formulated flame retardant chemicals—RDP, BPADP, and decaBDE—is based upon the lowest benchmark achieved by the chemical s constituents and breakdown products. This is to address concerns with the hazards associated with the use of the chemical constituents in manufacture (both due to worker exposure and releases to the environment and into local communities) and with the degradation of the formulated chemical into more hazardous byproducts. 

Pentaerythritol is used in self-extinguishing, non dripping, flame-retardant compositions with a variety of polymers, including olefins, vinyl acetate and alcohols, methyl methacrylate, and urethanes. Phosphoms compounds are added to the formulation of these materials. When exposed to fire, a thick foam is produced, forming a fire-resistant barrier (see Elame retardants) (84—86). 

Useful materials incorporating fire-retardant additives are not always straightforward to produce. Loadings of 10% are common, and far higher levels of flame retardants are used in some formulations. These concentrations can have a negative effect on the properties and functions for which the materials were originally intended. Product-specific trade-offs are generally necessary between functionaUty, processibiUty, fire resistance, and cost. 

Flame-retardant additives are capable of significant reduction in the ha2ard from unwanted fires, and techniques are now available to quantify these improvements. Combined with an understanding of fire-retardant mechanisms, polymer-retardant interactions, and reuse technology, formulations optimi2ed for pubHc benefit and manufacturing practicaUty can be selected. 

Powdered antimony pentoxide is used primarily in plastics. Stabilizers used to prevent the particles from growing are caustic, and can react with the halogen in the formulation. This can result in color formation and a lower flame-retarding efficiency of the system. 

Alumina trihydtate is also used as a secondary flame retardant and smoke suppressant for flexible poly(vinyl chloride) and polyolefin formulations in which antimony and a halogen ate used. The addition of minor amounts of either zinc borate or phosphoms results in the formation of glasses which insulate the unbumed polymer from the flame (21). 

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. 

Poly(vinyl chloride). PVC is a hard, brittle polymer that is self-extinguishing. In order to make PVC useful and more pHable, plasticizers (qv) are added. More often than not the plasticizers are flammable and make the formulation less flame resistant. Flammability increases as the plasticizer is increased and the relative amount of chlorine decreased, as shown in Table 7. The flame resistance of the poly(vinyl chloride) can be increased by the addition of an inorganic flame-retardant synergist. 

Alumina Trihydrate. Alumina trihydrate is usually used as a secondary flame retardant in flexible PVC because of the high concentration needed to be effective. As a general rule the oxygen index of flexible poly(vinyl chloride) increases 1% for every 10% of alumina trihydrate added. The effect of alumina trihydrate on a flexible poly(vinyl chloride) formulation containing antimony oxide is shown in Figure 5. 

Olefin Polymers. The flame resistance of polyethylene can be increased by the addition of either a halogen synergist system or hydrated fillers. Similar flame-retarder packages are used for polypropylene (see Olefin polymers). Typical formulations of the halogen synergist type are shown in Table 15 the fiUer-type formulations are in Table 16. 

Cblorina.ted Pa.ra.ffins, The term chlotinated paraffins covers a variety of compositions. The prime variables are molecular weight of the starting paraffin and the chlorine content of the final product. Typical products contain from 12—24 carbons and from 40—70 wt % chlorine. Liquid chlotinated paraffins are used as plasticizers (qv) and flame retardants ia paint (qv) and PVC formulations. The soHd materials are used as additive flame retardants ia a variety of thermoplastics. In this use, they are combiaed with antimony oxide which acts as a synergist. Thermal stabilizers, such as those used ia PVC (see vinyl polymers), must be used to overcome the inherent thermal iastabiUty. 

Tetrachlorphthalic Anhydride and Tetrachlorphthalic Acid. Tetrachlorphthalic anhydride [117-08-8] (TCPA) is manufactured by the ferric chloride catalyzed chlorination of phthalic anhydride. The relatively low chlorine content and the lower flame retardant efficiency of the aromatic chlorides limit use to unsaturated polyester resin formulations that do not requite a high degree of flame retardancy. 

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). 

One noteworthy neurotoxic response was demonstrated in laboratory pyrolysis studies using various types of phosphoms flame retardants in rigid urethane foam, but the response was traced to a highly specific interaction of trimethylolpropane polyols, producing a toxic bicycHc trimethylolpropane phosphate [1005-93-2] (152). Formulations with the same phosphoms flame retardants but other polyols avoided this neurotoxic effect completely. 

Effects on Visible Smoke. Smoke is a main impediment to egress from a burning building. Although some examples are known where specific phosphoms flame retardants increased smoke in small-scale tests, other instances are reported where the presence of the retardant reduced smoke. The effect appears to be a complex function of burning conditions and of other ingredients in the formulation (153,156,157). In a carehil Japanese study, ammonium phosphate raised or lowered the smoke from wood depending on pyrolysis temperature (158). Where the phosphoms flame retardant functions by char enhancement, lower smoke levels are likely to be observed. 

Table 1. Water-Soluble Flame-Retardant Formulations, % Composition...

THP—Amide Process. THP has also been made directly from phosphine [7803-5-27] and formaldehyde. The THP so generated contains one less mole of formaldehyde than either THPC or THPOH. It can be used in a THP—amide flame-retardant finish. The pad formulation contains THP, TMM, methylol urea, and a mixed acid catalyst (93—95). 

Combination Flame Retardant—Durable Press Performance. Systems using THPC, urea, and TMM can be formulated to give fabrics which combine both flame-retardant performance and increased wrinkle recovery values (80). Another system employs dimethylol cyanoguanidine with THPC under acidic conditions (115). Both of these systems lead to substantial losses in fabric tensile and tearing strength. 

Antlblaze 19. Antiblaze 19 (Mobil), a flame retardant for polyester fibers (134), is a nontoxic mixture of cycHc phosphonate esters. Antiblaze 19 is 100% active, whereas Antiblaze 19T is a 93% active, low viscosity formulation for textile use. Both are miscible with water and are compatible with wetting agents, thickeners, buffers, and most disperse dye formulations. Antiblaze 19 or 19T can be diffused into 100% polyester fabrics by the Thermosol process for disperse dyeing and printing. This requires heating at 170—220°C for 30—60 s. 

THPC—Amide—PoIy(vinyI bromide) Finish. A flame retardant based on THPC—amide plus poly(vinyl bromide) [25951-54-6] (143) has been reported suitable for use on 35/65, and perhaps on 50/50, polyester—cotton blends. It is appUed by the pad-dry-cure process, with curing at 150°C for about 3 min. A typical formulation contains 20% THPC, 3% disodium hydrogen phosphate, 6% urea, 3% trimethylolglycouril [496-46-8] and 12% poly(vinyl bromide) soUds. Approximately 20% add-on is required to impart flame retardancy to a 168 g/m 35/65 polyester—cotton fabric. Treated fabrics passed the FF 3-71 test. However, as far as can be determined, poly(vinyl bromide) is no longer commercially available. 

The molten salts quickly dissolve the metal oxides at high temperatures to form a clean metal surface. Other uses are as catalysts and in fire-retardant formulations (see Flame retardants). 

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... 

The salt ia this case is tetrakis(hydroxymethyl)phosphonium chloride [124-64-1]. The corresponding sulfate salt [55566-30-8] is also produced commercially as are urea-containing formulations of both salts. The latter formulations are actually used to flame retard the textiles (see Flame retardants FOR textiles). 

Flame-Retardant Resins. Flame-retardant resins are formulated to conform to fire safety specifications developed for constmction as well as marine and electrical appHcations. Resins produced from halogenated intermediates (Table 5) are usually processed at lower temperatures (180°C) to prevent excessive discoloration. Dibromoneopentyl glycol [3296-90-0] (DBNPG) also requires glass-lined equipment due to its corrosive nature. Tetrabromophthahc anhydride (TBPA) and chlorendic anhydride (8) are formulated with ethylene glycols to maximize fiame-retardant properties reaction cycle times are about 12 h. Resins are also produced commercially by the in situ bromination of polyester resins derived from tetrahydrophthahc anhydride... 

Table 5. Molar Component Ratio Used in Flame-Retardant Formulations...

Melamine—Formaldehyde Resins. The most versatile textile-finishing resins are the melamine—formaldehyde resins. They provide wash-and-wear properties to ceUulosic fabrics, and enhance the wash durabiHty of flame-retardant finishes. Butylated melamine —formaldehyde resins of the type used in surface coatings may be used in textile printing-ink formulations. A typical textile melamine resin is the dimethyl ether of trimethylolmelamine [1852-22-8] which can be prepared as follows ... 

Minor and potential new uses include flue-gas desulfurization (44,45), silver-cleaning formulations (46), thermal-energy storage (47), cyanide antidote (48), cement additive (49), aluminum-etching solutions (50), removal of nitrogen dioxide from flue gas (51), concrete-set accelerator (52), stabilizer for acrylamide polymers (53), extreme pressure additives for lubricants (54), multiple-use heating pads (55), in soap and shampoo compositions (56), and as a flame retardant in polycarbonate compositions (57). Moreover, precious metals can be recovered from difficult ores using thiosulfates (58). Use of thiosulfates avoids the environmentally hazardous cyanides. 

Flame retardants (qv) are incorporated into the formulations in amounts necessary to satisfy existing requirements. Reactive-type diols, such as A/ A/-bis(2-hydroxyethyl)aminomethylphosphonate (Fyrol 6), are preferred, but nonreactive phosphates (Fyrol CEF, Fyrol PCF) are also used. Often, the necessary results are achieved using mineral fillers, such as alumina trihydrate or melamine. Melamine melts away from the flame and forms both a nonflammable gaseous environment and a molten barrier that helps to isolate the combustible polyurethane foam from the flame. Alumina trihydrate releases water of hydration to cool the flame, forming a noncombustible inorganic protective char at the flame front. Flame-resistant upholstery fabric or liners are also used (27). 

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