Antimony, condensation polymers

Phosphorus-based flame retardants are usually more suitable for engineering plastics that undergo charring than for commodity polymers. In some plastics, such as PC-ABS or poly(phenylene oxide)-HIPS blends, phosphorus-based flame retardants are more effective then halogenated flame retardants. Antimony trioxide, which is a part of halogen-containing formulations, is a Lewis acid and may destabilize some condensation polymers. Furthermore, the impact properties of engineering polymers may suffer due to the presence of powdery antimony trioxide. 

Either mechanism can be used to describe how antimony—halogen systems operate in both the condensed and vapor phases. In the condensed phase a chat that is formed during the reaction of the polymer, antimony trioxide, and the halogen reduces the rate of decomposition of the polymer therefore, less fuel is available for the flame (16). 

In this regard, it should be noted at this point that one of the products identified by CGC/MS from these pyrolysis reactions was SbBr3- Furthermore, the data presented concerning the importance of the polymer substrate in the degradation of the DBDPO and the proposed chain radical transfer mechanism [7] would suggest that the condensed phase chemistry could be much more important in antimony oxide/organohalogen flame retardant systems than had been previously thought. 

Stevenson, R. W Poly condensation rate of poly (ethylene terephthalate) - II. Antimony trioxide catalyzed polycondensation in static thin films on metal surfaces, J. Polym. Sci., PartA-1, 1, 395-407 (1969). 

Zinc borates are predominately a condensed phase fire retardant. In a halogenated system such as flexible PVC, it is known to markedly increase the amount of char formed during polymer combustion whereas the addition of antimony trioxide, a vapor-phase flame retardant, has little effect on char formation. Analyses of the char show that about 80%-95% of the antimony is volatilized, whereas the majority of the boron and zinc from Firebrake ZB remains in the char (80% and 60%, respectively).48-56 The fact that the majority of the boron remains in the condensed phase is in agreement with the fact that boric oxide is a good afterglow suppressant. The mode of action can be summarized in the following equation (not balanced). 

Fenimore and Jones (12) report die first of their investigations into the modes of inhibiting polymer flammability. They show that chlorine substituted in polyethylene inhibits by affecting the pyrolysis of the condensed phase, but the pair of reactants, antimony plus a little chlorine, poisons the flame. Bromine is more effective than chlorine because it also poisons the flame. They speculate that halogen seems necessary to vaporize Sb from Sb203. 

The most abundant species in the equilibrium vapor over condensed metals are generally atoms as shown by Knudsen effusion mass spectrometry. The relative abundance of the homonuclear diatomic molecules was determined to be between 10 and 10 percent if they are detectable. Exceptions are bismuth and antimony. The dimer partial pressure over liquid bismuth at temperatures below 1000 K exceeds that of the monomer [83, 164, 165]. The tetramer is the most abundant species over liquid antimony [85]. Other polyatomic homonuclear species have so far been observed under equilibrium conditions for some of the alkali metals, as well as the group Ib, IVb, and Vb metals. Particularly large polymers up to 667 and Sn7 were detected for germanium [84,166,167] and tin [168],... 

Water and carbonated beverage bottles are made predominantly from poly(ethylene terephthalate) (PET). The polymer is made by condensation reaction of ethylene glycol with either terephthalic acid or its dimethyl ester. The process in practice includes three steps prepolymer formation, melt condensation to increase viscosity, and solid-state polymerization at 180-230°C to yield a resin with an average molecular weight that is high enough for use as bottle resins. Antimony trioxide is used as a catalyst in polymerization (Duh, 2002). 

Borates with zinc, calcium, magnesium, melamine or barium as the cation, combine char formation with endothermic decomposition as a dual mechanism that provides an efficient flame retardant system. Although the exotherm reduction is not as great as that achieved with ATH, there is enough endotherm to delay the initiation of the polymer exotherm by as much as 100 °C in some systems. It is this endothermic reaction in the polymer condensed phase and the formation of a glassy char that makes borate products good s mergists with the fire retardant antimony trioxide. 80% of the boron from zinc borate remains in the char after PVC combustion. 

Antimony compounds are generally used as fire retardants in synergistic combinations with halogen compounds. The mechanism of action is not well understood, but may be associated with effects due to the release of the hydrogen halide, acting possibly both in the condensed phase to modify the decomposition of the polymer and in the gas phase as a flame quencher. 

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