cal complex about 20 miles from Kobe, near Osaka. A fine chemicals plant there shut down because of water shortages, says a spokesman. But there was little damage at the site. The complex also houses fine chemicals research and environmental health science labs. Spokesmen for Hoechst, Exxon Chemical, Schering-Plough, and Searle, Monsanto's drug division—all of which have sales offices in Osaka—report their facilities suffered little or no structural damage. And they have accounted for their employees. George Peaff
Two men indicted for CFC smuggling into U.S. A federal grand jury in Miami has indicted two men for illegally importing 126 tons of chlorofluorocarbons (CFCs) for sale in the U.S. The case is the largest seizure yet of illegally imported ozone-depleting chemicals, says the U.S. Attorney's Office in Miami. The accused men face up to 20 years in jail and fines of more than $2 million if convicted. A black market in CFCs has developed as supplies of the soon-to-bebanned chemicals decrease and their prices increase. The federal government set up an interagency task force last year to try to curtail the illegal activity (C&EN, Oct. 31,1994, page 4). "We've been very concerned for quite a while," says Stephen R. Seidel, director of the Environmental Protection Agency's Stratospheric Protection Division. "This is the first major case, so we are extremely pleased. We anticipate there will be more." Under the Montreal Protocol on Substances That Deplete the Ozone Layer, industrialized nations must phase out CFC production by Jan. 1, 1996 (stockpiled or recycled CFCs can still be used after that). In the U.S., EPA requires any company that produces or imports the chemicals to have a permit called a consumption allowance. And Congress has imposed an excise tax—cufrently $5.35 per lb—on the sale of ozone-depleting chemicals to encourage users to switch to substitutes. The Miami indictment charges Adi Dara Dubash and Homi N. Patel with conspiring to violate EPA and Internal Revenue Service regulations. They alleg-
edly imported seven shipping containers, each filled with 1,200 cylinders— each cylinder containing 30 lb of CFC-12 (CC12F2)—under the pretext that the chemicals were just passing through the U.S. on the way to Mexico. "It's perfectly legal to bring CFC-12 into the U.S. without EPA consumption allowances if you are not going to sell it here," notes George H. White II, the Customs Service special agent in Miami who investigated the case. "In this instance, [Dubash and Patel] had all the paperwork completed as if they were going to ship it back out to a foreign company. But when the truck showed up to take the containers out of the bonded facility here in Miami, we followed and found they did not take them to a shipping company." The Alliance for Responsible Atmospheric Policy, a coalition of CFC users and producers, has urged industry and the public to be suspicious of CFCs offered for sale at prices below the excise tax. "We hope to see more of these indictments so people realize the government is serious," says David J. Stirpe, alliance executive director. "The black market reduces the incentive to shift to alternatives and penalizes legitimate companies who are complying with U.S. laws." Pamela Zurer
Long, stable acetylenic carbon chains prepared
capping each end with a trifluoromethyl (CF3), nitrile (C^N), or other group. His results, accumulated over 10 years, indicate the capped chains are surprisingly stable. The chains also have very useful properties. They are highly soluble in most organic solvents—"a novel feature for any form of carbon," he notes—and thus might be used to make carbon coatings. Because of their triple bonds, the chains pack more electron density than any other form of carbon or known organic compound. So they might be the ultimate in molecular wires for molecular electronic devices. And since they have less thermal stability than graphite or diamond, they might be excellent precursors for diamond synthesis and graphite coatings. Lagow's team, which includes collaborators at the University of Southern California and Texas A&M University, College Station, prepares linear "sp" carbon by laser vaporization of graphite—the same technique used by some groups to prepare fullerenes. Using a laser to vaporize graphite in the presence of CF3 or C=N radicals in his lab leads to carbon chains capped with CF3 or C=N groups. When these capping radicals are absent, fullerenes such as C60 and C70 form. The team concludes from its experiments that laser vaporization produces unstable carbon-chain diradical species. When free radicals are present, they cap the carbon-chain species and allow their isolation. But in the absence of capping radicals, the acetylenic chains condense to form fullerenes or particulate material known as fullerene soot.
They said it couldn't be done, so Richard J. Lagow did it. In a paper published last week in Science [267, 362 (1995)], Lagow, a chemistry professor at the University of Texas, Austin, and 10 coworkers reveal how they synthesized and identified a new material consisting of linear chains of 300 to 500 "naked" carbon atoms. Unlike the carbon atoms in diamond, graphite, or fullerenes, those in Lagow's carbon chains are sp-hybridized, so the chains contain alternating single and triple bonds. Another group reported acetylenic carbon chains of this sort, with as many as 32 carbon atoms, as far back as 1972. But linear chains with hundreds of sp-hybridized carbon atoms were thought to be too unstable to prepare and isolate because of their reactivity. Lagow stabilizes these long acetylenic chains, whose structure has been con- Lagow (left) and one of his coworkers, firmed by a variety of techniques, by graduate student Han-Chao Wei.
JANUARY 23,1995 C&EN 7
NEWS OF THE
WEEK
The experiments in Lagow's lab produce mixtures of carbon chains, which haven't yet been separated. To gain a better understanding of the molecules, the researchers used conventional solution-phase methods to prepare model compounds that contain acetylenic chains of eight, 16, 24, and 28 carbon atoms. These chains, they find, are stable to at least 130 °C. An X-ray crystal structure of the C8 compound shows the chain is slightly curved. Lagow believes much longer chains, present as diradicals in vaporization experiments, could form spiral structures that would undergo a series of
"zipperlike" cross-linking reactions, similar to Diels-Alder reactions, to give fullerenes or fullerene-like materials. However, cautions another chemist familiar with the work, this "spiral zipper hypothesis" hasn't been substantiated by experiment. Lagow says his linear carbon material should be considered a new elemental form of carbon—in the same realm as graphite, diamond, and fullerenes/ nanotubes. Not everyone agrees. "This is the best chemistry ever done in my laboratory," he says. But he admits "not everyone is going to believe [our results]." Ron Dagani
Process change boosts polyethylene production BP Chemicals has unveiled a simple modification in its gas-phase process for making polyethylene that promises, for a modest investment, to more than double a reactor's capacity, slashing unit production costs. Introduction of the "high-productivity technology" by the London-based chemicals arm of British Petroleum follows several years of development. The work included X-ray imaging at the company's corporate research center in Sunbury, near London, and process runs at its 110 million-lb-per-year polyethylene test plant at Lavera on the French Mediterranean coast. A key problem with gas-phase fluidbed polyethylene polymerization has
Modified polyethylene process reactor throughput
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JANUARY 23,1995 C&EN
been removal of heat from the reactor, where reaction temperatures commonly run from 75 to 105 °C. This forms an intrinsic reactor bottleneck, limiting production capacity. BP Chemicals tackled this problem by turning to vaporization. Its new design enhances heat-exchange capacity so gases given off during polymerization are cooled and liquefied. The resulting liquids are separated and fed by a special injection nozzle back into the reactor, where they vaporize, absorbing heat from the system. Enough heat is removed to eliminate the bottleneck, the company says, enabling reactor output to more than double. The process works with any currently used catalysts and will accommodate metallocene catalysts being deincreases veloped throughout the industry. The company has applied for patents on the gas-phase technology in all major countries. The application, WO94/28032, was published in early December under the international Patent Cooperation Treaty. The firm plans to license the technology to other producers. BP Chemicals will install the technology in a retrofit of its 275 millionlb-per-year polyethylene plant at Grangemouth, Scotland, boosting capacity to 353 million lb by the end of 1995 and to 440 million lb in 1997, says
Michael Buzzacott, chief executive officer of the polymers and olefins division. Buzzacott says BP is sensitive to the issue of expanding capacity, noting the chemical industry has "just been through three terrible years" of low or nonexistent profitability. "But our customers at Grangemouth are now on allocation, and polyethylene markets, particularly in Europe, are growing quickly," he adds. There is a high probability the firm also will install the new process during expansion of a joint venture in Indonesia. Licensing General Manager Martin Howard claims the new technology will make obsolete all polyethylene processes except gas-phase polymerization. Whether it will or not, it offers polymer makers a new option in deciding whether to enlarge current facilities or build new ones. BP Chemicals is the second-largest licensor worldwide of gas-phase technology for making polyethylene, behind Union Carbide. Howard calculates BP's technology has been used in 27% of new plants built in the past decade, versus 38% for Carbide's. BP expects gas-phase technology to take an even larger share of new plants in the next investment cycle. "Our goal is to overtake Union Carbide to become number one," he says. Patricia Layman
FDA drug approval rate still draws industry fire The Food & Drug Administration made major improvements last year in its review speed for new drug applications. But the pharmaceutical industry still expresses concern about FDA's performance. FDA's just-issued annual summary of drug approval statistics shows significant improvement in review times in 1994 for approval of 85 new drugs and biological products. The median review time for 23 approved vaccines and biological products was 12.2 months, about half that in 1993. But of the 23, only one—ReoPro, a monoclonal antibody marketed by Centocor for use in angioplasty—was a new molecular entity (a product containing an active substance never marketed in any form in the U.S.). The agency's median time for approval of 52 new drugs (those not in
