Polymer char formation

The industrial value of furfuryl alcohol is a consequence of its low viscosity, high reactivity, and the outstanding chemical, mechanical, and thermal properties of its polymers, corrosion resistance, nonburning, low smoke emission, and exceUent char formation. The reactivity profile of furfuryl alcohol and resins is such that final curing can take place at ambient temperature with strong acids or at elevated temperature with latent acids. Major markets for furfuryl alcohol resins include the production of cores and molds for casting metals, corrosion-resistant fiber-reinforced plastics (FRPs), binders for refractories and corrosion-resistant cements and mortars. 

Phosphoms compounds are effective flame retardants for oxygenated synthetic polymers such as polyurethanes and polyesters. Aryl phosphates and chloroalkyl phosphates are commonly used, although other compounds such as phosphonates are also effective. The phosphoms compounds can promote char formation, thereby inhibiting further ignition and providing an efficient thermal insulation to the underlying polymer. 

Boronic acids (69 and 70) (Fig. 45) with more than one boronic acid functionality are known to form a polymer system on thermolysis through the elimination of water.93 Specifically, they form a boroxine (a boron ring system) glass that could lead to high char formation on burning. Tour and co-workers have reported the synthesis of several aromatic boronic acids and the preparation of their blends with acrylonitrile-butadiene-styrene (ABS) and polycarbonate (PC) resins. When the materials were tested for bum resistance using the UL-94 flame test, the bum times for the ABS samples were found to exceed 5 minutes, thereby showing unusual resistance to consumption by fire.94... 

The symposium was planned as a state-of-the-art meeting, focusing on the basic science. Program areas included high heat polymers, fire performance of polymers, hazard modeling, mechanism of flammability and fire retardation, char formation, effects of surfaces on flammability, smoke assessment and formation mechanisms, and combustion product toxicity. 

An efficient flame retardant effect was demonstrated with 2-mil zinc coatings on polyphenylene oxide-polystyrene blends (Notyl) by Nelson (21). The action may relate to enhanced char formation by chemistry specific to this blend. However, other metal coatings on some other polymers also appeared to contribute a measurable flame retardant effect. 

The principles needed to design a polymer of low flammability are reasonably well understood and have been systematized by Van Krevelen (5). A number of methods have been found for modifying the structure of an inherently flammable polymer to make it respond better to conventional flame retardant systems. For example, extensive work by Pearce et al. at Polytechnic (38, 39) has demonstrated that incorporation of certain ring systems such as phthalide or fluorenone structures into a polymer can greatly increase char and thus flame resistance. Pearce, et al. also showed that increased char formation from polystyrene could be achieved by the introduction of chloromethyl groups on the aromatic rings, along with the addition of antimony oxide or zinc oxide to provide a latent Friedel-Crafts catalyst. 

It is well known that char formation during polymer burning is an important mechanism by which polymers resist burning. For example Van Krevelen (1-2) has shown that a correlation exists between the oxygen index (OI) of a polymer containing no heteroelements and the amount of char it forms when pyrolyzed in the absence of air. As shown in Table I, a similar correlation is seen to hold for a number of common engineering thermoplastics. 

FACTOR Char Formation in Aromatic Engineering Polymers... 

The mechanism of the action of the phosphonate as a flame retardant is generally believed to be decomposition into acid fragments which contribute to char formation. These acidic species catalyze decomposition of the polyester, and give rise to species which on reaction with the phosphorus moiety cause char formation. TGA curves of the copolymers confirm that the incorporation of phosphorus into the polymer increases the char residue (Figure 4). These curves, however, show little evidence that the presence of phosphorus has any effect upon the temperature or rate of decomposition of the polyester. The curves are all fairly similar up to about 450°C. After that point, the amount of residue is proportional to the amount of phosphorus in the terpolymer. 

Fuel, oxygen, and high temperature are essential for the combustion process. Thus, polyfluorocarbons, phosphazenes, and some composites are flame-resistant because they are not good fuels. Fillers such as alumina trihydrate (ATH) release water when heated and hence reduce the temperature of the combustion process. Compounds such as sodium carbonate, which releases carbon dioxide when heated, shield the reactants from oxygen. Char, formed in some combustion processes, also shields the reactants from a ready source of oxygen and retards the outward diffusion of volatile combustible products. Aromatic polymers, such as PS, tend to char and some phosphorus and boron compounds catalyze char formation aiding in controlling the combustion process. 

Flame retardants impart to the polymers some ability to resist ready combustion. Since fuel, oxygen, and high temperature are essential for the combustion of polymers, the removal of any of these prerequisites retards combustion. Flame retardants act through a variety of mechanisms including char formation and combination with free radical species that promote further combustion, through release of water. 

Conversion of polymers and biomass to chemical intermediates and monomers by using subcritical and supercritical water as the reaction solvent is probable. Reactions of cellulose in supercritical water are rapid (< 50 ms) and proceed to 100% conversion with no char formation. This shows a remarkable increase in hydrolysis products and lower pyrolysis products when compared with reactions in subcritical water. There is a jump in the reaction rate of cellulose at the critical temperature of water. If the methods used for cellulose are applied to synthetic polymers, such as PET, nylon or others, high liquid yields can be achieved although the reactions require about 10 min for complete conversion. The reason is the heterogeneous nature of the reaction system (Arai, 1998). 

Char also shields the reactants from oxygen and in addition retards the outward diffusion of volatile combustible products. Aromatic polymers tend to char, and some phosphorus and boron compounds tend to catalyze char formation. 

Furthermore, the effect of hydrated fillers on polymer fire retardancy will depend not only on the nature of the filler, including its particle characteristics (size, shape, and purity) and decomposition behavior, but also on the degradation mechanism of the polymer, together with any filler/ polymer interactions that might occur, influencing thermal stability of the polymer and possible char formation. 

The resulting blends were shown to possess enhanced flammability and mechanical properties. The cone calorimeter data shown in Table 8.1 indicate that the highest reduction in the PHRR was obtained for the Pebax system where a reduction of 65%-70% in PHRR was reported. The reduction in heat release was obtained by enhanced char formation. The char reduces the escape of small volatile molecules to the gas phase, which in turn reduces the amount of heat release feedback to the polymer surface. 

There has been a great recent market demand for halogen-free fire-retardant polymers. Zinc borates are also multifunctional fire retardants in halogen-free polymers. They can promote char formation, reduce the Rate of Heat Release, smoke evolution, carbon monoxide generation, and afterglow combustion. When used in conjunction with metal hydroxides, they can also display synergy in fire test performance. 

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). 

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