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The replacement of established chemistries with newer ones is one of the classic drivers of change in the chemical industry, and one of the current hotbeds of this kind of change is the replacement of brominated flame retardants in polymer formulations. The process is transforming existing flame-retardant suppliers and creating opportunities for new companies to enter the market.
As a result, many polymer fabricators are trying to avoid brominated flame retardants altogether. Even brominated flame-retardant suppliers are diversifying their offering to include nonbrominated retardants. In fact, sometimes they lead the charge. Great Lakes Chemical is voluntarily phasing out penta- and octa-BDEs by the end of next year. Because there are no other U.S.-based producers of penta- and octa-BDEs, and because the Environmental Protection Agency has pledged not to allow new uses of the products, the phaseout is almost like a nationwide ban. Angelo C. Brisimitzakis, executive vice president for flame retardants and brominated performance products at Great Lakes, says the phaseout is made possible by the clean bill of health granted by EPA for Firemaster 550, a replacement for penta-BDE in flexible polyurethane applications. A phosphorus-bromine blend, Firemaster 550 passed third-party lab tests for persistence, bioaccumulation, and toxicity. "EPA has been--rightfully so--concerned that the alternatives were worse than the products they were replacing," Brisimitzakis acknowledges. Great Lakes will end penta- and octa-BDEs manufacturing and scale up production of Firemaster 550 by the end of next year at its El Dorado, Ark., plant. Albemarle Corp., Great Lakes's main competitor in brominated flame retardants, doesn't produce penta-BDE and phased out octa-BDE in the mid-1990s. Fred Gastrock, a plastics additives consultant with BRG Townsend in Mount Olive, N.J., says that despite the hoopla, the phaseout of the two products isn't as earth shattering as would be an exit from deca-BDE, a styrenics additive that is produced in the highest volume of the PBDEs. "They didn't touch deca," he says. "They just agreed not to produce materials that are in decline or not produced at all." He notes that out of the 165 million lb of brominated flame retardants consumed in North America in 2001, about 35% were PBDEs, and 85 to 90% of that was deca. Brisimitzakis says there's no need to phase out deca-BDE. "Deca is very persistent, but it doesn't readily bioaccumulate, and it is not toxic," he says. To producers, the brominated flame-retardants controversy boils down to a trade-off between unknown illnesses and death or injury from fire. "We help save lives and give people time to get out of fires," Brisimitzakis says. "I view it as taking medicine. If you take any kind of medicine, there are side effects. The side effects of PBDEs are persistence in the environment." "What we want to do is offer solutions that are sustainable in the long term." IRONICALLY, BROMINATED flame retardants are still a growing market. According to BRG Townsend's Gastrock, the global flame-retardants market has annual volume of about 2.0 billion lb valued at $2.2 billion. Halogenated materials--including halogenated phosphorus flame retardants--make up 35 to 40% of this by volume and 55% by value. Brominated flame retardants alone account for 25% of the volume and 35% of the value. Both the entire flame-retardants industry and the brominated piece of it are growing at 4% annually. Luc Van Muylem, global business director for flame retardants at Albemarle, points out that brominated flame retardants are still growing, largely because of increasingly stringent fire safety standards in Europe and the U.S. California requires flame retardants in polyurethane foam mattresses. And proposed laws like the American Home Fire Safety Act would make similar requirements national. "You have a continually increased use of flame retardants because of the drive for safety, and underneath that you have the increased concern for flame retardants," Van Muylem notes. Moreover, observers say, there are about 50 different brominated flame retardants. So far, as in the case of Firemaster 550, much of the replacements have been different brominated flame retardants replacing PBDEs. "In brominated flame retardants as a whole, I don't see much threat over the near term," Gastrock says. Replacing a brominated flame retardant with a nonbrominated one isn't usually a drop-in substitution. "You really have to start playing with the polymer if you want to get away from halogenated flame retardants," Van Muylem says. For example, he says, polystyrene, high-impact polystyrene, and acrylonitrile-butadiene-styrene require halogenates to acheive appropriate flame retardancy. However, polycarbonate/ABS or polyphenylene oxide/ABS blends naturally form a protective char when they burn, so a phosphorus-based flame retardant can be used. Furthermore, Van Muylem says, substitutes like aluminum trihydrate or magnesium hydroxide can be employed, but the retardants have to comprise up to 50 to 60% of the product being protected, a dosing level that can affect performance properties. And brominated flame-retardant makers aren't exactly holed up in the Alamo: They, too, are diversifying their businesses away from brominated materials. About five years ago, both Albemarle's and Great Lakes's flame-retardant businesses were 100% bromine based. Now, through acquisition and internal development programs, roughly 35% of their sales come from nonbrominated flame retardants. In July, Albemarle purchased Rhodia's organophosphorus and ammonium polyphosphate flame-retardants business for $65 million. Van Muylem says the new business will strengthen the company's position in rigid polyurethane applications and bring it into flexible polyurethane, a potential boon given stricter fire regulations. In 2001, Albemarle purchased Germany's Martinswerk, which offers aluminum trihydrate and magnesium hydroxide, products popular in wire and cable applications. Great Lakes purchased FMC's flame-retardants business in 1999, giving it phosphorus-based systems used in polycarbonate and polycarbonate/ABS blends. The company has also been expanding an antimony oxide/mineral flame-retardant facility in Mexico. "We have three different platforms of technology, and we let our customers decide what they want," Brisimitzakis says. Ciba Specialty Chemicals, not a brominated flame-retardant supplier, has targeted flame retardants for growth and sees an opportunity because bromine is under scrutiny. The company has its internally developed Flamestab NOR hindered amine line of flame retardants, and last year it purchased DSM's melamine flame-retardants business. "The brominated products have some advantages," says Felix Meyer, global head of Ciba's plastics additives business. "They wouldn't be so successful if they hadn't. The producers of brominated products are following the strategy of shifting from products that are under attack to products that are less environmentally critical. What we want to do is offer solutions that are sustainable in the long term. We are on the way to becoming the largest provider of nontraditional flame-retardant solutions in the industry." INDUSTRY OBSERVERS see Ciba as a likely candidate to buy the Akzo Nobel phosphorus flame-retardants business that is up for sale. "I would expect that Ciba would be in the running," Gastrock says. "That would make them a heavy hitter in nonhalogenated flame retardants." Brisimitzakis observes that the flame-retardants business Great Lakes purchased from FMC was originally Ciba's. "They probably regret the day they sold that business to FMC, who then sold it to us," he says. Despite the investments in new chemistry, producers believe brominated flame retardants will be around for a long time. Brisimitzakis makes the distinction between necessary additives like brominated flame retardants and aesthetic ones like pigments. "If you are creating something cosmetic, something that makes something fluorescent green, and it has some environmental issues, why have it? You don't have to be fluorescent green. Be purple." But where they can be, brominated flame-retardant producers have shown that they, too, are willing to be purple.
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