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Editorial Green Chemistry C G Green Chemistry August 1999 G83 he week starting June 28, 1999 marked an important and enjoyable annual event in the Green Chemistry world: the presentation of the Presidential Green Chemistry Challenge Awards at the National Academy of Sciences in Washington DC, USA. Following the award presentations, the 3rd Annual Green Chemistry and Engineering Conference provided a forum for award winners and other scientists and engineers to report their results and engage in state-of-the-art discussions.As usual, Paul Anastas, Tracy Williamson, and Joe Breen were responsible for much of the organization of this event, which is sponsored by the US Environmental Protection Agency, American Chemical Society, American Institute of Chemical Engineers, Chemical Manufacturers Association, Council for Chemical Research, Green Chemistry Institute, National Institute of Standards and Technology, National Research Council, National Science Foundation, US Department of Energy, and the Organization for Economic Cooperation and Development.I offer congratulations to the award winners, the organizers, sponsors and conference participants.This year’s Presidential Awardees are briefly listed here, and I look forward to a series of articles in Green Chemistry from the various scientists and engineers who contributed to and administered these programs: l Professor Terry Collins of Carnegie Mellon University won in the academic category for his iron-based peroxide activators that have broad applications to oxidations in the pulp and paper industry, water disinfection, and laundry bleaching.Terry has a background in coordination chemistry and catalysis, and has become a major force in the development of green oxidants. Biofine Inc.’s plant converting paper mill sludge into levulinic acid received a 1999 Presidential Green Chemistry Award Tl The Small Business Award went to Biofine, Incorporated for a process that converts cellulosic biomass into levulinic acid, a useful building block for many chemical products.The biomass feedstocks for this process include paper mill sludge, unrecyclable paper waste, waste wood and certain agricultural residues. An industry–government consortium has conducted the work on high value-added derivatives of levulinic acid. It was a pleasure to see that my old friend and former colleague Joe Bozell was one of the lead scientists on this program.l The Alternative Synthetic Pathways Award went to Eli Lilly and Company for designing a green synthesis of a compound currently under testing for a variety of central nervous system diseases. Key aspects of this work included replacing a CrO3 oxidation with an air oxidation, and the use of a biocatalytic transformation using specially identified yeast.I had the pleasure of chairing the conference session where Dr. Benjamin Anderson described the work done by the Lilly group. l Nalco Chemical Company received the Alternative Reaction Conditions Award for developing a new water-based process for the manufacture of liquid polymers. Applied to the preparation of acrylamide polymers that are important for waste-water treatment, this method avoids the exposure hazards and energy costs associated with dry (powder) polyacrylamide samples, and also avoids the use of organic solvents and surfactants associated with the alternative ‘water-in-oil’ preparations of these materials.l Dow AgroSciences received the award for Designing Safer Chemicals for the development of Spinosad, a selective, low-risk insecticide (registered by EPA as a reduced risk pesticide). A fermentation process using a naturally occurring microorganism isolated from a Caribbean soil sample produces Spinosad.Spinosad has demonstrated remarkable selectivity in targeting pests that attack cotton, trees, turf, fruits, vegetables and ornamental plants without harming 70–90% of beneficial insects and predatory wasps.Spinosad presents little risk to the environment since it does not leach, bioaccumulate, volatilize or persist in the environment. These properties make it a valuable tool for pest management. For a fuller discussion of this award see the short article by Anastas et al. on page G88 of this issue of Green Chemistry.At the same awards ceremony, the Kenneth G. Hancock Memorial Scholarship in green chemistry was presented to W. Clayton Bunyard of the University of North Carolina, Chapel Hill. Bunyard’s research centers on environmentally benign syntheses of perfluoropolyethers (PFPEs) and new uses for these materials. One such synthesis uses carbon dioxide instead of ozone-depleting CFCs as the solvent.New uses of PFPEs include so-called ‘fouling-release coatings’ for ocean-going ships. These coatings prevent marine organisms from adhering to ships, in contrast to traditional antifouling coatings (i.e. alkyltin reagents) that are toxic and that accumulate in water and marine life. One theme that has been common for many of the awards and conference presentations is the following: green chemistry does not hurt the simple economic bottom line while it helps the environment.Instead, many green processes provide considerable economic advantages C G G84 Green Chemistry August 1999even before the savings in environmental costs have been computed. How can this be? In public debates in the US, environmentally benign industrial practices are often automatically associated with higher costs to industry.This false, inverse relationship between public good and industrial benefit was certainly in evidence during early debates over automobile emissions and safety, with sides being chosen on political rather than economic grounds. It is important to spread the news that, time and again, green innovation goes hand-in-hand with economic benefits—lower raw materials costs, less wasted material, more energy-efficient processes, more efficient synthetic chemical routes, fewer separation steps.I believe that most industrial processes are the brainchildren of earlier eras. They used then state-of-the-art chemistry to prepare the products. Any reason for a complete, modern technical re-evaluation should lead to processes that offer greatly enhanced environmental and economic attributes. This certainly is true for ‘old’ chemistry such as that sometimes found in commodity chemicals production, but also occurs for pharmaceutical chemistry, where companies can become locked into a particular synthetic route because of the need for the entire route to be subject to regulatory approval.We heard a wonderful talk in Washington by Sam L. Nguyen of Roche Colorado Corporation, who along with my old friend Chris Roberts and other team members, developed a green and economically beneficial synthesis of Cytovene®, an important drug against cytomegalovirus (CMV). CMV plagues AIDS and transplant patients. Reducing the number of chemical processing and isolation steps from 6 to 2 and cutting the number of reagents and intermediates from 22 to 11 were just some of the ways that the costs (economic and environmental) were reduced, allowing sustainable and cost-effective scale-up to meet increasing patient need.Of course, often there are capital expenditures that are necessary to capture the economic and environmental benefits of new processes, and large capital spending does entail risk. Therefore, the companies that move forward with new green processes are to be congratulated, and should enjoy considerable economic benefit just as our global ecosystem benefits from the greening of their industry. Green processes that can be retrofitted into existing plants may allow the faster route to capturing value. Conferences such as the 3rd Annual Green Chemistry and Engineering Conference and the 1999 Gordon Conference on Green Chemistry allow industrial, academic and government scientists and policymakers to interact and cross-fertilize each other’s efforts. James K. Bashkin, St. Louis, MO, USA, July 1999. C G Green Chemistry August 1999 G85

ISSN:1463-9262    

DOI:10.1039/a906917h

出版商:RSC    

年代:1999

数据来源: RSC

摘要:

C G Green Chemistry August 1999 G87 O B I T U A R Y It is with great sadness that we have to report the death on 19 July 1999 of Joe Breen—one of the Editorial Board members of Green Chemistry. Only a short time ago, on the evening of 28 June 1999, in the Great Hall of the National Academy of Sciences, Joe was presented with the Distinguished Service to Green Chemistry Award from the President of the American Chemical Society.For the hundreds of people in attendance that evening, many of whom participate in the Green Chemistry research, education or industrial applications, the award was welcome and deserved recognition for a driving force in the development of Green Chemistry. As inscribed on the award itself, Joe Breen was recognised for his ‘extraordinary leadership and tireless efforts in the advancement of Green Chemistry globally through research, education and outreach’.Joe Breen was the executive director of the Green Chemistry Institute and served as the Chair of the Committee on Environmental Improvement of the American Chemical Society. In both of these roles Joe promoted green chemistry as a new and innovative approach to environmental protection. The decade of the 1990s has seen green chemistry develop from its inception and infancy into a growing recognised area with activities around the world.In these years Joe Breen was a leading ambassador for the expansion of green chemistry. He was a founding member of the editorial advisory boards of the journal, Green Chemistry. As a co-chair of the Green Chemistry and Engineering Conference, Joe guided the conference to demonstrate the broad applicability of green chemistry throughout academia, industry and government.Joe’s interests consistently centred on breaking down barriers through the use of green chemistry. Green chemistry knows no borders was a centrepiece of Joe’s approach as evidenced by his almost evangelical tours which spread the word of green chemistry across national boundaries.One could just as easily find Joe addressing a group of industrial chemists in Oakash (Wisconsin) or Eire (Pennsylvania) as addressing researchers and students in Hefei (China), Venice (Italy) or St. Petersburg (Russia). Joe Breen’s twenty years in the U.S. Environmental Protection Agency (EPA) helped to inform him on exactly how important and urgent Green Chemistry is at this stage of the environmental movement.During his time at EPA, Joe was involved in the many regulatory aspects of the Toxic Substances Control Act including playing a major part in the EPA’s Lead Program. He won the Agency’s highest honour, the EPA Gold Medal, for designing and implementing the ‘Test Our Kids for Lead’ Program and was co-editor of the book ‘Lead Poisoning: Exposure, Abatement and Regulation’.But while valuing the impacts and necessity of regulatory command-and-control approaches to cleaning up the waste of the past, Joe Breen was more interested in looking forward to the future. With the passage of the Pollution Prevention Act of 1990, Joe focussed his efforts on the prevention of waste before it is ever generated by the proper design of the process in the first place.In 1993, the book ‘Pollution Prevention in Industrial Processes: The Role of Process Analytical Chemistry’ by Breen and Dellarco illustrated how process analytical chemistry can prevent the formation of undesirable by-products and parasites before they accumulate. In 1995, Joe Breen organised the Design-for-Environment symposium at the American Chemical Society Meeting in Washington D.C.with over 140 speakers on Green Chemistry and related topics. It would be the first of many symposia that Joe organised and/or participated in. Because of his strong desires to support educational activities, Joe devoted considerable time and effort to teaching green chemistry at such diverse locations as Trinity College (Washington D.C.), Hood College (Maryland) and the Venice Summer School on Green Chemistry in Italy. A major project that Joe was recently involved in is the incorporation of Green Chemistry principles into the popular ACS chemistry textbook Chemistry in Context.The importance of green chemistry to achieve the goals of industrial ecology was a central theme of Joe Breen’s work.One of the illustrative examples that Joe played a major role in promoting is the use of supercritical and liquid CO2 in the area of garment care. From funding of basic research (during his time both at EPA and as Executive Director of GCI) to promoting and catalyzing industrial and academic interactions in this area, Joe served as a conduit in bringing this industrial ecology technology from the lab bench to commercial fruition. Joe will be sadly missed by his friends and colleagues within Green Chemistry and beyond. In 1998, he published a paper in the Journal of Cleaner Production entitled “Green Chemistry and Design for Environment: The Heart and Soul of Industrial Ecology”. From the contributions that Joe Breen has made to Green Chemistry it is easy to see why his colleagues often refer to him as “the heart and soul of green chemistry”. Paul T. Anastas, Chief, Industrial Chemistry Branch, Office of Pollution Prevention and Toxics, US EPA, Washington, USA. Joe Breen— heart and soul of Green Chemistry

ISSN:1463-9262    

DOI:10.1039/a906793k

出版商:RSC    

年代:1999

数据来源: RSC

摘要:

19 9 9 G R E EN CH E M I S TR Y AWA RD S C G G88 Green Chemistry August 1999 Paul Anastas, Mary Kirchchoff and Tracy Williamson of the USA EPA present the first in a series of short profiles on this year’s Green Chemistry Award winners Controlling insect pests is essential to maintaining high agricultural productivity and minimising monetary losses. Synthetic organic pesticides, from a relatively small number of chemical classes, play a leading role in pest control today.The development of new and improved pesticides is necessitated by increased pest resistance to existing products, along with stricter environmental and toxicological regulations. To meet this need, Dow AgroSciences has designed spinosad, a highly selective, environmentally-friendly insecticide.Discovery During the 1980s, Lilly Research Laboratories (Indianapolis, USA) operated a program directed at finding new natural products that possessed utility in the pharmaceutical and agrochemical industries. Soil samples from all over the world were collected, fermented, extracted, and screened in a variety of assay systems. Wherever possible, the soil samples were collected from unusual habitats, to improve the chances of finding new microorganisms.During the course of this fermentation screening program, extracts from the fermentation broth of a soil sample, collected in 1982 on a Caribbean island, were found to be active in a mosquito larvicide assay and against the southern army worm (Spodoptera eridania). The microorganism was identified as Saccharopolyspora spinosa, and it produced a family of new macrolides (molecules containing a macrocyclic lactone), now called spinosyns, of which the primary components are spinosyn A and spinosyn D.An extract of the fermentation broth that contains this naturally occurring mixture is called spinosad. Products such as Tracer® Naturalyte® Insect Control and Precise® contain spinosad as the active ingredient.Mode of action Spinosad demonstrates both rapid contact and ingestion activity in insects, which is unusual for a biological product. The mode of action of spinosad (although not fully elucidated) is characterized by excitation of the insect nervous system, leading to involuntary muscle contractions, prostration with tremors, and paralysis. These effects are consistent with the activation of nicotinic acetylcholine receptors and prolongation of acetylcholine responses through a novel mechanism.Insect spectrum Spinosad has been tested extensively on a global basis since 1990 and found to provide effective control of pests in the insect orders Lepidoptera, especially the tobacco bollworm (Heliothis virescens), the cotton bollworm (Helicoverpa zea), American bollworm (H.armigera) and armyworms (Spodoptera spp.). Environmental fate Spinosad presents a favourable environmental profile. It does not leach, bioaccumulate, volatilize, or persist in the environment. Spinosad will degrade photochemically when exposed to light after application. Because spinosad strongly adsorbs to soils, it does not leach through soil to groundwater when used properly and no buffer zones are required by the United States Environmental Protection Agency.Nontarget toxicology Spinosad is relatively low in toxicity to mammals and birds, and, although moderately toxic to fish, this toxicity represents a reduced risk to fish when compared with many synthetic insecticides in use. In addition, 70-90% of beneficial insects and predatory wasps are left unharmed by spinosad. Conclusion The unique mode of action of spinosad, coupled with a high degree of activity on targeted pests, low toxicity to non-target organisms (including many beneficial arthropods), and resistance management properties make spinosad an excellent new tool for integrated pest management.Further reading Thompson, G.; Hutchins, S. (1999) Spinosad - a new class of fermentationderived insect control agents. Pesticide Outlook 10(2), 78-81. SPINOSAD - a new natural product for insect control Spinosad is a mixture of spinosyn A and spinosyn D Visit the Green Chemistry homepage FREE electronic access to full contents of Issue 1 http://www.rsc.org/greenchem

ISSN:1463-9262    

DOI:10.1039/a906794i

出版商:RSC    

年代:1999

数据来源: RSC

摘要:

C G Green Chemistry August 1999 G89 N E W S Cleaner fuels Gas-to-liquids technology ...Chevron and Sasol in gas-to-liquids joint venture Chevron and Sasol have signed an agreement to create a new global joint venture founded on gas to liquids (GTL) technology, one of the most promising prospects for clean fuel development in the 21st century. The application of GTL technology to the enormous gas reserves located throughout the world could become the preferred method to commercialize such natural gas resources, many of which are remote and cannot easily be made commercial.A proposal was announced in April 1998, in which Chevron and Sasol outlined plans to build a GTL products plant in Nigeria. Design and engineering continue on the GTL facility, which will be capable of converting natural gas into synthetic crude oil for further processing into commercial products, principally high quality diesel and naphtha.The initial feasibility study has recently been expanded to increase target production from 20000 to 30000 barrels per day. The plant is expected to come on stream in 2003. The global joint venture would build on the foundation laid by Sasol, based on their Fischer–Tropsch technology and would utilize proprietary technologies of both companies— Chevron’s ISOCRACKING and Sasol’s Slurry Phase Distillate Process (http://www.chevron.com)....Rentech agreement with Texaco agreement Texaco and Rentech announced the signing of a Technical Services Agreement to research the integration of Rentech’s Fischer–Tropsch technology with Texaco’s gasification process.The goal is to produce a clean burning, sulfurand aromatic-free diesel fuel. The new Agreement calls for technical and developmental work to be carried out at the Rentech research and development facilities in Denver. The companies will work to maximize the hydrocarbon yield from synthesis gas produced by the Texaco gasification process.Rentech Inc. has also completed an agreement with Republic Financial Corp by which Rentech and Republic will jointly develop projects utilizing Rentech’s proprietary Fischer–Tropsch technology. The agreement represents a milestone for Rentech in its efforts to commercialize this technology (http://www.gastoliquids.com). New US sulfur specifications for gasoline On 1 May 1999, President Bill Clinton personally announced newly proposed federal standards for sulfur levels in gasoline that promise to allow automobiles to run 80% cleaner.The tough new specifications call for 30 ppm sulfur in gasoline, down from the The search for cleaner fuels is a major element of the drive to reduce the environmental impact of transport. Many approaches are being taken to reduce the pollution from vehicles.N E W S G90 Green Chemistry August 1999 C G current average of 340 ppm.The US Environmental Protection Agency estimates that this would take 3 million tonnes of pollution out of the air. The oil industry estimates that meeting the new sulfur targets using existing technology will require more than $6 bn in new US refinery investment. Refiners argue that the cost may be too high to meet the new sulfur standards.Biotechnological route to desulfurisation of fuels Energy BioSystems Corp is currently developing its $3 M biocatalytic technology to desulfurize gasoline at a target cost of 1 cent/gallon to 2 cents/gallon of gasoline. Energy BioSystems has already licensed its first unit for diesel fuel biodesulfurization to Petro Star Inc., a subsidiary of Arctic Slope Regional Corp, for their Valdez, AL, refinery.Energy BioSystems Corp of Houston is developing and commercializing biotechnology based processes for the petroleum refining and production industries. The company’s focus to date has been on developing biocatalytic desulfurization, a proprietary process involving the use of enzymes to remove sulfur from petroleum, including gasoline, diesel, and heavy and crude oils, while operating at mild temperature and pressure.The company is also pursuing opportunities to apply the principles of biocatalysis to the chemical industry, initially by developing a line of organosulfur products that are derived from its biodesulfurization process (http://www.energybiosystems.com). Shell Pura Diesel According to Shell, its Pura Diesel meets tough European emissions regulations six years early.A positive response from a London-based trial meant that the national launch was brought forward. Shell claims that Pura Diesel, with its unique formulation, helps meet growing demands from both the public and the government for cleaner fuels, and does so without compromising performance.The good news for the environment is that it contains 90% less sulfur than standard diesel, which means smoke and particulate pollution from exhaust pipes is greatly reduced. Further benefits for motorists arise because its additive package helps prevent carbon deposits building up in the engine, and gives improved combustion and protection against corrosion.Additionally, Pura Diesel is claimed to improve the fuel economy of a vehicle by up to 5–6% (http://www.shell.co.uk). Ultra-low-sulfur diesel Total Oil GB (Watford, Herts) is the producer of Ultra Low Sulfur Diesel (ULSD), which is being produced at its Lindsey Oil Refinery (LOR). Total Oil GB was the first oil company in the UK to introduce the modern cleaner diesel fuel when they introduced ‘City Diesel’ to tackle urban pollution, smoke and particulates (sooty particles) etc.ULSD was defined in the 1998 UK budget and Total Oil GB now produces it at LOR. It offers all the advantages of City Diesel, specifically in the following areas: 90% reduction in sulfur emissions, virtual elimination of black smoke, airborne particulate reduction greater than 30% and reduction of carbon dioxide and carbon monoxide emissions.Total ULSD is designed to be compatible with the latest catalyst equipped vehicles and those which qualify for the reduction in Vehicle Excise Duty. Bus company London United, an existing Total Oil GB customer, has recently announced that it is expanding its use of ULSD by switching its Kingston buses from conventional diesel to the new, green fuel.Low sulfur diesel in India The Indian Oil Corporation has just become the first in India to produce lowsulfur diesel via a hydrodesulfurization process. The capacity is 1.2 million tonnes per year and the refinery at Gujarat cost $127M. There are plans to set up further hydrodesulfurization units at three other refineries. Replacing MTBE Great West Energy and Exploration Inc.of Dallas, TX has entered into an agreement with Millennium Fuels USA that conveys the exclusive right to capitalize and participate in the only plants capable of producing one of the premier alternative replacements for the current refining industry standard additive, methyl-tertbutyl ether (MTBE). MTBE and other ether-type additives, utilized each day by the refining industry as octane enhancers and/or oxygenates, have come under attack due to their ground water contamination, harmful emissions and more importantly their possible effects on the human body.In March 1999, California became the first state in the US to ban the use of MTBE owing to its significant environmental risks. It is predicted that other states such as Massachusetts, New Hampshire, Connecticut, New York and New Jersey among others, will follow suit to ban the use of MTBE by 2000. The additive is produced from various natural hydrocarbons and raw ethanol through a patented process that produces an environmentally friendly octane additive/enhancer and oxygenate.New Fuels E85 from Ford The Twin Cities of Minneapolis/St Paul and Chicago will become test beds for efforts aimed at building sustainable ethanol (E85) infrastructure, and will also be part of a Ford coupon programme aimed at promoting the use of ethanol in flexible fuel vehicles (FFVs).FFVs allow drivers to run their vehicles on any combination of E85 and unleaded gasoline in the same tank. Ford Motor Co. plans to spend at least $1 M on developing retail alternative fuel infrastructure to help increase the use of these environmentally friendlier fuels.Ford is in partnership with the US Department of Energy to develop infrastructure in two pilot areas. In these test cities, Ford will provide eight $5 coupons to every purchaser of a 3 litre Ford Ranger pickup, which has FFV capability, targeting owners living within 15 miles of an E85 outlet.The E85 coupon programme is designed to encourage drivers of the Ranger FFV to visit the 10 E85 refuelling stations opening in Chicago and the up to 30 E85 stations planned for the Twin Cities area. By providing drivers with incentives to purchase E85 rather than gasoline, the Ford Motor Co. hopes to stimulate the use of E85 as an alternative to gasoline (http://www.ford.com). Ethanol blends ...in the US Ethanol currently accounts for less than 1% of US gasoline volume.Gasoline blending provides a market for 1.4 bn lbs/y of ethanol capacity and generates ethanol sales of $1.3 bn/y. The target of 10% ethanol content in gasoline by 1990 has never been approached owing to the price of ethanol and logistical constraints. Its use in hot weather is limited, and there are special requirements for storage and delivery of ethanol-containing gasoline which have led to marketing problems.The ethanol lobby portrays it as the longterm solution for reformulated gasoline, but gasoline producers and analysts do not agree. However, they do see a role for ethanol as a discretionary octane improving additive, and as an oxygenate in some markets. If the US subsidy on ethanol were removed it would probably not beGreen Chemistry August 1999 G91 NEWS C G used at all.It also receives additional subsidies in some US states. ...and in Brazil Brazil was one of the pioneers of the ethanol car, using ethanol derived from the sugar cane industry. In the 1970s and 1980s there were hundreds of thousands of ethanol-powered cars in the country; nowadays there are only a couple of thousand.However, the price of sugarcane ethanol in Brazil is very low at the moment, and pollution fears combined with the risk of substantial job losses in the sugar industry have led the government to persuade General Motors and Ford to restart production of alcohol cars. Fiat and Volkswagen are already producing them in Brazil.The government has announced that it will increase the amount of alcohol added to petrol from 24% to 26% and that taxi drivers will no longer enjoy tax breaks on petrol-fuelled cars, but will continue to do so if they use ethanol as a fuel. Fuel cells Fuel cells for Canada Petro-Canada, Ballard Power Systems and Methanex have announced the signing of a Memorandum of Understanding under which the three companies will work together to prepare for the establishment of a commercially viable fuel distribution network to meet the expected market demand for fuel cell vehicles.Petro-Canada, Ballard and Methanex will collaborate in laying the groundwork for a pilot project involving the supply and distribution of appropriate fuel, starting with methanol to facilitate the introduction of fuel cell vehicles (http://www.petro-canada.ca).Shell Hydrogen Shell is the first of the major oil companies to state its commitment to bringing fuel cells to market, with its formation of Shell Hydrogen. Shell has reached an agreement with a subsidiary of Daimler Benz involving co-operative research into fuel cell power for motor vehicles (http://www.shell.co.uk).Delphi and BMW announce fuel cell developments Delphi Automotive Systems (Troy, Michigan, USA) and BMW have signed a development agreement to produce vehicles that use a solid oxide fuel cell as an auxiliary power unit and that have the potential of being clean, high power generation vehicles. Under the development agreement, BMW and Delphi are jointly developing a fuel cell system that will be used as an auxiliary power unit for gasoline engines.This will allow BMW to offer more features more efficiently with the potential to reduce the emissions of an internal combustion engine. Delphi will develop the fuel cell system and BMW will integrate the unit into a vehicle. The solid oxide fuel cell unit will provide more energy into the vehicle to enhance the electrical systems.Delphi and BMW plan to produce the solid oxide fuel cell unit in the near future. The solid oxide fuel cell unit has the ability to increase the electric power within a vehicle to offer more features in the most efficient way. Additionally, it provides tremendous potential to reduce the emissions of the internal combustion engine (http://www.delphiauto.com).Hydrogen fuel cell vehicles Zevco, a British manufacturer of hydrogen fuel cell powered vehicles, has announced that it will become listed on the Easdaq and Nasdaq stock exchanges this year. This will allow the company to meet the expected increase in demand. The company is negotiating a contract to supply some vans to the UK Royal Mail, and has recently introduced the first zeroemission taxi to New York following its launch of the zero emission London Millennium Taxi.Other tests for short journey vehicles (e.g. taxis to and from airports) are being held, and the company expects to start manufacturing in the US soon. More on cars Automatic shut-off Honda has announced that it will market a scooter, the Giorno Crea DeLuxe, which automatically shuts off when stopping.The price will be around £1000. The scooter emits about half the levels of pollution allowed in Japan, and is also claimed to be more fuel-efficient than similar scooters. Germany stalls car recycling The European Union has been working on a plan to make car producers bear the cost of recycling old cars. However, the European Automobile Manufacturers Association (ACEA) have been lobbying strongly against this proposed law.The law has finally been defeated amidst accusations of Germany buckling under pressure from its powerful car lobby. ‘It is quite clear that the way the German presidency handled the end-of-life car directive was nothing less than a disgrace,’ Peter Jorgensen, spokesman for Environment Commissioner Ritt Bjerregaard, told a news briefing.The legislation would only have added 0.5% to the price of a new car, Jorgensen added. German Chancellor Gerhard Schroeder said recently that an appeal from Volkswagen AG had prompted his country to think again. Schroeder is a former member of VW’s supervisory board. Britain and Spain, both with significant car manufacturing capacity, said they were sympathetic to the Fuel cell taxi cab (London) from Zevco First generation fuel cell transit bus from Ballard Power SystemsNEWS C G G92 Green Chemistry August 1999 German position.It will now be up to the next EU president, Finland, an enthusiastic supporter of the proposals, to find a compromise. Environment ministers next meet in October, though Finland has said it would consider dealing with the proposal before then.CO2 deal between EU and Korea, but not yet with Japan The European Commission has struck a deal with Korea to reduce pollution from cars in a voluntary scheme. This would mean that average fuel consumption would be reduced from the current average of 7.7 litres/100 km to around 6. The European Commission has said that it is seeking to achieve this by 2008, the Koreans by 2009.Japan has not yet agreed, claiming that it has a different balance of the large and small car markets to the other countries, and that the target will affect it differently. The European Union has threatened to impose restrictions if a voluntary agreement is not reached soon. New products Coalescent solvent for specialist coatings Chemoxy International plc, of Middlesbrough, UK, has launched a new coalescent solvent which has been formulated to assist the film formation properties of speciality wood coatings, finishes, varnishes and lacquers.The low VOC (volatile organic chemical) content, low odour solvent is also well suited for use in decorative paints and coatings, adhesives, screen printing inks and leather coatings.Called Estasol BG, the coalescent solvent is the latest addition to Chemoxy’s rapidly expanding range of low toxicity solvents. The new high purity solvent is biodegradable, colourless and has a high flash point of 75°C. Compatible with a wide range of resins including polyvinylacetate, nitrocellulose and polyvinylbutyrate, Estasol BG is ideal for formulators looking to produce the ‘next generation’ of quick evaporation, environmentally friendly coating products.Forming and stamping fluids Solutia Inc., St Louis, USA, is introducing a new series of water-based forming and stamping fluids, the Glacier 5000 series, as new members of its metalworking fluid family. These unique products provide the benefits of oil in a water-based fluid, and serve as an alternative to the oil-based forming that currently dominates the market.Developed from breakthrough protein technology, Glacier 5000 is designed for both ferrous and non-ferrous metals. The bright and clear amber liquid uses water-based chemistry and does not contain oil. As a result, it can be easily cleaned or washed off parts using water or traditional cleaning systems.Glacier 5000 works in a wide range of applications with a broad array of applicators. It also helps parts and dies stay cooler. In addition, Glacier 5000 promotes a cleaner, safer work environment. Glacier 5000, and all Glacier fluids, are thoroughly tested for health effects. Glacier 5000 holds the safest rating for toxicity, and has a low odour. In addition, the fluid is biodegradable and recyclable, and contains no hazardous waste constituents (http://www.solutia.com).High-temperature carbon dioxide-absorbing ceramics Toshiba, Japan, has developed a ceramic material that can absorb carbon dioxide at 450–700°C through a chemical reaction after contact. This material is made from lithium zirconate which can absorb 400 times its volume of carbon dioxide— 10 times better than conventional materials.Thus, it is possible to absorb carbon dioxide from high-temperature high-pressure gases, applicable for example in coal-burning power generation plants, manufacturing sites and cars. The recovered carbon dioxide can also be utilized. Research is underway to lower the production cost and widen the applications. New processes Copper sulfate by nitric acid-catalyzed air oxidation A process for making copper sulfate has been developed by a group from the Northwest University, China, that does not evolve sulfur dioxide during the process to pollute the environment.Waste copper wire or other copper waste is heated with water, sulfuric acid and a catalytic amount of nitric oxide at 85°C and 8 kPa, with four air inlets to give an even and ample oxygen supply.The crystalline product is collected by filtration, and the mother liquor is recycled for another run of the production. A water-based process for manufacturing optical brighteners Optical brighteners have been traditionally manufactured by dissolving cyanuric chloride in a volatile solvent such as acetone and reacting this with a sulfonated amine.Ultimately the solvent which is required to effectively get the water-insoluble cyanuric chloride in an active form, is recycled but it can be avoided altogether in some cases through the use of surfactants. Hickson and Welch have recently extended the cleaner technologies to the manufacture of optical brighteners for the detergent industry. The major reasons for this are removing solvent costs, avoiding handling flammable solvents, avoiding VOC containment costs and adding value through the exploitation of more environmentally friendly technologies. Hickson and Welch now operate a water-based manufacturing process which eliminates the use of some 3000 tonnes/year of solvent (Environmental Business Magazine, May 1999).Awards ICI wins environmental award ICI’s newly formed Synetix business has won the Queen’s Award for Environmental Achievement for Hydecat, its unique process for treating sodium hypochlorite produced from waste chlorine streams.The Hydecat process, as it is known, converts sodium hypochlorite (bleach) from a potentially harmful mixture to a benign common salt solution and oxygen. Hydecat technology is essentially automatic and guaranteed for at least three years.ICI’s first commercial units were installed in 1993 and since then further improvements have been made both to the process and to the catalyst. More than 20 customers in 9 countries have successfully applied the Hydecat technology. Customer savings are impressive: one customer has reduced the cost of destruction of hypochlorite from £300000/y to £30000/y.Dexter recognized with five 1999 patent awards Dexter Electronic Materials (Industry, California, USA) received five 1999 patent awards for patents issued in 1998. The patent for stabilized nitric acid compositions claims a stabilizer that reduces the decomposition of acid when used to strip tin or tin/lead solder from printed circuit boards.Benefits to Dexter customers include dramatically extended bath life and ease of waste treatment relative to competitive processes. The patent for propargyl ether-containing compositions useful for underfill applications claims the use of aromaticC G Green Chemistry August 1999 G93 N EWS propargyl ethers as an underfill resin chemistry. The described resins can be cured to produce hydrophobic, high glass transition thermosets with no evolution of volatiles.The patent for perfluorinated hydrocarbon polymer-filled adhesive formulations and uses claims the use of perfluorinated hydrocarbon filler in die attach adhesives. Products based on this technology provide customer value in the form of reduced potential for radio frequency cross talk and ease of application.The patent for maleimide-containing formulations and uses claims the use of hydrophobic resin combinations useful in the preparation of high temperature, blister resistant laminates for printed wiring boards. The patent for bleed resistant cyanate ester-containing compositions claims the use of novel bleed reduction additives in cyanate ester-based attach adhesives. Products based on this technology provide improved reliability and productivity. Catalysts Second-generation titanium dioxide photocatalyst A titanium dioxide photocatalyst which can operate at wavelengths higher than 420 nm and in the visible light region has been successfully developed by EcoDevice Company, Japan.With this material, most of the available energy from the sun can be utilized (compared with only 3% available at ultra-violet bands in the <400 nm region when using older photocatalysts).The company has already signed a contract with a manufacturing company, and expects to increase the production capacity to several kilograms per month soon. It is hopeful that the price will fall in due course (presently at more than Yen 20000/g). The photocatalyst can also be applied in solar cells to decompose water to generate clean hydrogen fuel.Reagent catalysts Contract Chemicals is developing a second generation of its Envirocats supported reagent catalysts. These can replace traditional catalysts associated with unacceptable levels of waste and by-products. They can be used instead of Friedel–Crafts and Brønsted acid and oxidation catalysts. They are non-toxic, non-corrosive and inert relative to homogeneous catalysts like aluminium trichloride.Contract recently commissioned a £5 M fine chemical plant expansion at Knowsley, UK. Catalytic synthesis of tributyl citrate Tributyl citrate (TBC) is a non-toxic plasticizer, with superior compatibility and plasticization properties to impact, cold, light and water resistance.Since phthalate plasticizers are well regulated because of their undesirable environmental impact, TBC has become the material of choice. Conventionally, TBC is made with concentrated sulfuric acid as catalyst for esterification. However, due to the low yield, corrosion to equipment and environmental pollution caused by the use of sulfuric acid, newer catalysts have been developed.A homemade activated carbon-supported heteropoly acid catalyst has been prepared by a team from the Fujian Institute of Research on Structure of Matter, China. When reacting citric acid and butanol in the presence of 22.5% of the catalyst at 145°C, up to 98% pure TBC is obtainable (see article by Becky Allen on phthalates in toys in this issue of Green Chemistry).Biotechnological processes The recent patents are Merck’s for a microbial conversion of glycerol to dihydroxyacetone and Genencor’s for the microbial synthesis of quinic acid from glucose. DuPont and Genencor have jointly developed, using recombinant DNA technology, a process to create a single microbe that converts sugar from corn starch into the monomer propane-1,3-diol using a biotransformation process.The new technology will enable production of propane-1,3-diol at a cost approaching that of ethylene glycol, the monomer for production of poly- (ethylene terephthalate). The company is taking this further with the biological processing of propane-1,3-diol to the polyester poly(trimethylene terephthalate) (PTT). DuPont claims the PTT has enhanced properties compared with conventional polyester.The technology will be commercially available by 2004 and DuPont plans to build a 20000 tonnes/y plant. Recently, Shell of Holland has been developing PTT for use in the textile and carpet industries. Other research groups in various European countries and in China are also studying such production technology. DuPont builds new fluoropolymer plant for supercritical carbon dioxide process DuPont Co.(Wilmington, Delaware, USA) has begun construction of a $40 million, 2.5 million lb/year development and manufacturing facility to make meltprocessable fluoropolymers using a process based on supercritical carbon dioxide. It is planned that $275 million will be spent over the next seven years if the trials are successful.The company has already been testing the technology at a $2-million pilot plant it brought on stream in 1999 at the DuPont Experimental Station in Wilmington. It expects the new unit to open in late 2000 and produce fluorinated ethylene propylene (FEP) and perfluoroalkoxy resin (PFA). The company plans to demonstrate the technology for two to three years before building a larger plant. The technology gives DuPont the ability to make new grades of polymer which have specialized properties. It also promises to be more efficient, more flexible, and less costly than existing processes. The process came about from a partnership between DuPont and Joseph DeSimone, William R. Kenan, Jr. Distinguished Professor of Chemistry and Chemical Engineering at both the University of North Carolina at Chapel Hill and North Carolina State University in Raleigh, N.C. He is a pioneer in polymer synthesis using supercritical fluids. DuPont has supported his research since 1990. DuPont’s Teflon FEP is widely used for plenum cable insulation because of its excellent insulating properties, fire resistance, and light weight, which makes it easier to string over long distances. A new production technology based on supercritical carbon dioxide promises more specialized grades and improved process economics. DeSimone’s group reported the first successful homogeneous free radical polymerization in an inert supercritical fluid (SCF) in 1992 (S c i e n c e, 1992, 2 5 7, 945). Since then, he has expanded synthesis technology to include dispersion, cationic, ring-opening metathesis, step-growth, and additional heterogeneous p o l y m e r i z a t i o n s .

ISSN:1463-9262    

DOI:10.1039/a906795g

出版商:RSC    

年代:1999

数据来源: RSC

摘要:

The continuous microwave reactor He was the principal inventor of the continuous microwave reactor (CMR) which operates by pumping organic solvents and reactants through a microwave-transparent vessel held in a microwave zone.1 The monitoring and controlling operations are performed outside the microwave zone and allow organic reactions to be performed rapidly and continuously at elevated pressures and temperatures.With this unit, several difficult reactions, including preparations of highly reactive monomers and the iron-chelating drug deferiprone, have been carried out cleanly and easily in his laboratory. Chris was instrumental in the technology transfer and CSIRO’s commercial partner, Milestone MLS (Germany and Italy), is now F EAT U R E G94 Green Chemistry August 1999 here were fewer than five papers on microwave-assisted organic synthesis when Dr Chris Strauss entered the field in 1988.The state-ofthe- art equipment consisted of rudimentary domestic microwave ovens and relatively primitive reaction vessels susceptible to explosions. There was little fundamental knowledge about the effects of microwave energy on organic molecules and it was difficult to obtain a uniform energy distribution and to control and measure temperature. In short, the technique had shown promise, but was dangerous.Chris thought that if equipment could be developed to allow the organic chemist to carry out reactions safely and controllably, microwave technology could become a valuable tool for cleaner chemical processing. manufacturing and distributing units globally under licence.Microwave batch reactor for chemical synthesis Chris was also the principal inventor of the microwave batch reactor (MBR), a system that can be operated at pressures up to 100 atmospheres and temperatures up to 265 °C under rigorously controlled and monitored conditions in the laboratory.2 The vessels are fabricated from inert materials.Reactions are monitored from within the microwave zone and the computer-driven system has the capability for stirring, sample withdrawal and reagent introduction, as well as for rapid post-reaction cooling. Microwave power input can be carefully controlled and is continuously variable. This reactor is expected to become important for organic synthesis, particularly through the application of new techniques such as differential heating and concurrent heating and cooling.Summary of Chris Strauss’ role in microwave chemistry Chris Strauss’ work has helped transform microwave chemistry from a laboratory curiosity into an important field, for which dedicated international conferences are now held regularly. His group is the only one to have designed, built and demonstrated microwave reactors for liquid phase organic synthesis at elevated temperature and pressure.Until these innovations, the equipment for carrying out preparative organic reactions had changed little over decades. Through the MBR and CMR, Chris has anticipated emerging requirements of industrial chemical reactors. His systems can be easily cleaned, an important consideration in lowering waste output.They also are portable, multi-purpose, self-contained and do not require an external boiler. Capabilities for just-intime processing and the materials of construction promote short turnaround times. The systems provide for remote, programmable operation and have the potential for tandem procedures including distillative reactions and coupling with catalytic membranes.The number of published refereed papers on microwave-assisted organic synthesis now exceeds 500. Chris is regarded not only as a pioneer in microwave-assisted organic chemistry, but as an authority in the field. By invitation, he has reviewed his work3 Award for microwave chemistry Susan Cumming from Howard Florey Institute describes the achievements of Chris Strauss from the CSIRO who has received the Royal Australian Chemical Institute (RACI) Inaugural Green Chemistry Challenge Award T C G Chris Strauss of CSIRO with his continuous microwave reactor.Green Chemistry August 1999 G95 F E AT U R E and presented plenary lectures at international microwave conferences in USA (1995), Canada (1997) and the Czech Republic (1998).Water as solvent Chris Strauss was first to recognise that high temperature water has properties that can be exploited for organic synthesis and product isolation.In a broad investigation facilitated by his microwave equipment, relatively modest differences in temperature afforded substantial variations in product distributions.4,5 High-temperature aqueous conditions had advantages over established synthetic procedures and were an attractive alternative to acidic or basic catalysts in organic solvents at lower temperatures.When addition of acid or base was necessary, less agent was usually required than for processes at and below 100 °C and the reactions often were selective. In some cases, the requirement was orders of magnitude lower. Significantly, inorganic salts account for the bulk of industrial chemical wastes.They contaminate soil and ground water and can lower the pH of atmospheric moisture and contribute to acid dew or acid rain. For cleaner production their minimisation is essential. Chris’s work represents a major advance in this context. The preparation of the important synthetic building block, 3-methylcyclopent- 2-enone, is a good example.6 Earlier workers had used strong base in high concentration for the moderately yielding preparation and generated substantial amounts of salt in their work-up.His method employed up to 400 times more dilute base. Competing reactions were suppressed, salt formation was lowered and the product was obtained in the highest yield so far reported. The industrial viability of the process was established using a heat-jacketed autoclave and a continuous microwave reactor.Resin-based isolation methods Chris was also first to develop resin adsorption and ion-exchange techniques for isolation and purification of products synthesised under aqueous conditions.6 Advantages of such non-extractive processes for clean processing include ease of use, high throughput and low waste.The resin can be readily recycled, as can the solvent used for desorption. The preparation of 3-methylcyclopent- 2-enone exemplified his strategy for cleaner production.6 Microwave technology, high-temperature aqueous media and resin-based isolation procedures were combined to overcome difficulties with established methods and to obtain products in high yield.Catalytic membranes Chris has also recognised that catalytic methods can avoid the use of stoichiometric inorganic reagents. He has developed methods for retaining catalytic metals on porous glass tubing and investigated these novel materials as catalysts for Heck-type couplings.7 Advantages of palladium on porous glass included resistance to aerial oxidation, ease of manufacture, mechanical strength and thermal stability, recyclability, negligible loss of palladium into the reaction mixture and obviation of air- and temperature-sensitive ligands.He has used palladium on porous glass in conjunction with microwave heating to catalyse reactions. High turnover numbers were obtained in some cases and he also discovered a new tandem coupling– oxidation process.New and improved reactions Uncatalysed hydrogen transfer Chris also discovered that aldehydes and ketones can be reduced to the corresponding alcohols by transfer hydrogenation at high temperature with ethanol, n-propanol or isopropanol as hydrogen donors in the absence of catalysts and base.8 The potential environmental benefits include inexpensive, renewable reagents, minimal waste and that no inorganic salts are introduced or formed.Catalytic etherification Most methods for etherification use either strongly acidic or basic conditions and C G Pump controller H.P. pump ReactantsF E AT U R E C G G96 Green Chemistry August 1999 have well documented disadvantages. The nearly 150 year old Williamson synthesis is still the most common procedure.It involves substitution of an alkyl halide (RX) by a strongly basic alkoxide or phenoxide (e.g. KOR or NaOR) and so is unsuitable if base catalysed elimination of HX from RX can compete. A stoichiometric amount of waste salt (KX or NaX) is also produced. Chris has invented a catalytic etherification that produces little organic waste and that can be carried out without the addition of acid or base.9 For a symmetrical ether, an excess of alcohol (ROH) and a catalytic amount of RX are heated (see Scheme 1).A solvolytic displacement reaction between RX and ROH affords R2O along with HX or its elements (hereafter referred to as HX; equation 1). The liberated HX reacts with another molecule of ROH to form water and to regenerate RX (equation 2). If the rates of these forward reactions are comparable, the concentration of HX will be low throughout and that of RX will remain relatively constant.Although HX and RX are stoichiometric reactants or products in equations 1 and 2, they do not appear in the sum, equation 3. The nett process involves condensation of two molecules of ROH to give R2O plus water. It requires participation by the counterion X- and utilises ostensibly neutral conditions.For efficient operation, CSIRO—where Chris Strauss works CSIRO (Commonwealth Scientific and Industrial Research Organisation) is the largest R&D organisation in Australia, employing over 7000 staff in areas such as agriculture, minerals and energy, manufacturing, communications, construction, health and the environment. Chris Strauss works within the Molecular Science Division of CSIRO that employs over 300 staff in Melbourne and Sydney.Its research programs are designed to assist the development of industries related to the medical, pharmaceutical, chemicals, polymers, water treatment and waste management sectors of the Australian economy. For further information on CSIRO in general see http://www.csiro.au and on the Molecular Science Division in particular see http://www.molsci.csiro.au X- should be a good leaving group (to satisfy equation 1), an effective nucleophile (to accommodate equation 2) and a weak base to minimise competing elimination reactions.Bromide and iodide possess these properties. It appears that a critical participatory role for the counterion of the acid has not previously been envisaged or recognised.RX + ROH " R2O + HX (1) HX + ROH " RX + H2O (2) 2 ROH " R2O + H2O (3) Scheme 1. Pathway for catalytic ether synthesis The potential for commercial exploitation of the reaction is currently under consideration. New tandem arylamidation Chris has also developed a single-pot synthesis for N-aryl amides which can be conducted as a domino reaction or a tandem sequence.10 Before this reaction, there were few, if any, useful literature methods for obtaining, in a single step, N-aryl amides from aromatic compounds which do not possess an amino function.The new method greatly simplifies the Hoechst–Celanese process for the manufacture of paracetamol. The opportunities for clean processing include atom economy, obviation of isolation and purification of intermediates, savings in time, raw materials and solvent consumption and avoidance of multiple work-up and cleaning operations.Avoidance of heat transfer oils A key step in the preparation of quinolone antibacterial agents involves the formation of an amino ketone ring system by intramolecular cyclisation of a diethyl N-(aryl)aminomethylene malonate derivative at temperatures near 250 °C.To obviate intermolecular reactions, the condensations are usually carried out in high dilution using heat transfer oils consisting of diphenyl ether or a eutectic mixture of diphenyl ether and diphenyl. However, such oils are unacceptable for clean chemical processing. Chris developed a thermal method for carrying out such Jacobs–Gould reactions in high conversion, rapidly, predictably and controllably, without a diluting heat transfer oil.11 He established a continuous process and demonstrated it on a laboratory scale. This was the first example of a Jacobs–Gould reaction having been performed in such a manner.The procedure accommodates high throughput, is energy efficient, is low polluting and offers easy work-up.Indole transformations Direct, preparative methods utilising high-temperature aqueous media, were developed for indole and indole-2-carboxylic acid from ethyl indole-2-carboxylate.12 Yields were excellent for these reactions, which were carried out in 1 hour or less, at temperatures up to 270 °C, in the microwave batch reactor. Avoidance of undesirable copper salts, high boiling organic bases and heat transfer oils made the methods environmentally benign.References 1 T. Cablewski, A. F. Faux and C. R. Strauss, J. Org. Chem., 1994, 59, 3408; C. R. Strauss and A. F. Faux, US Patent 5 387 397, 1995; C. R. Strauss and A. F. Faux, Eur.Patent, 0437480, (1994). 2 K. D. Raner, C. R. Strauss, R. W. Trainor and J. S. Thorn, J. Org. Chem., 1995, 60, 2456; C. R. Strauss, K. D. Raner, R. W. Trainor and J. S. Thorn, Aust. Patent, 677876, 1997 and other applications pending. 3. C. R. Strauss and R. W. Trainor, Aust. J. Chem., 1995, 48, 1665. 4 L. Bagnell, T. Cablewski, C. R. Strauss and R. W. Trainor, J. Org. Chem., 1996, 61, 7355. 5 J. An, L. Bagnell, T. Cablewski, C. R. Strauss, and R. W. Trainor, J. Org. Chem., 1997, 62, 2505. 6 L. Bagnell, M. Bliese, T. Cablewski, C. R. Strauss, and J. Tsanaktsidis, Aust. J. Chem., 1997, 50, 921. 7 J. Li, A. W.-H. Mau and C. R. Strauss, Chem. Commun., 1997, 1275. 8. L. Bagnell and C. R. Strauss, Chem. Commun., 1999, 287. 9. L. Bagnell, T. Cablewski and C. R. Strauss, Chem. Commun., 1999, 283. 10 T. Cablewski, P. A. Gurr, K. D. Raner and C. R. Strauss, J. Org. Chem., 1994, 59, 5814. 11. C. R. Strauss, Aust. J. Chem., 1999, 52, 83. 12. C. R. Strauss and R. W. Trainor, Aust. J. Chem., 1998, 51, 703.

ISSN:1463-9262    

DOI:10.1039/a906796e

出版商:RSC    

年代:1999

数据来源: RSC

摘要:

C G Green Chemistry August 1999 G97 F OC U S O N . . . ony Barrett is Glaxo Professor of Chemistry and Director of the Wolfson Centre for Organic Chemistry in Medical Science at Imperial. Following his Ph.D. at Imperial under the tutorship of Professor Sir Derek Barton, Professor Barrett was immediately appointed to a lectureship at the College. In 1983 he moved to the USA for 10 years taking in Professorships at Northwestern University and Colorado State before returning to Imperial as Head of Organic Chemistry.Barrett’s research interests cover a wide range of organic chemistry ranging from identification of effective fungicidal agents to olefin metathesis, and optical and imaging materials. This article will focus on Barrett’s work with lanthanide triflates as clean catalysts of potential use to the fine chemicals industry.Tony Barrett’s interest in clean technology started following Kobayashi’s work in the early nineties describing lanthanide triflates as water tolerant Lewis acids. Barrett is also a keen advocate of Trost’s atom economy concepts and much of his work on clean technology has combined these two areas. Nitration One of Professor Barrett’s leading co-workers is Dr Chris Braddock who worked in the group as postdoctoral fellow until his recent appointment to a Lectureship at Imperial in October 1998.On arriving in the group in January 1996 he was challenged to nitrate toluene without using more than one mole equivalent of nitric acid, and without the use of sulfuric acid. Nitroaromatics are key chemical feedstocks for dyes, pharmaceuticals and plastics, but, their synthesis historically uses mixtures of fuming nitric acid and sulfuric acid leading to significant amounts of waste.More recently nitration has been carried out with nitric acid in the presence of Lewis acids such as BF3 but this approach is equally ‘unclean’ since stoichiometric amounts of ‘catalyst’ are required resulting in copious quantities of acidic waste.Rising to this challenge, Braddock’s application of lanthanide triflates to the nitration of toluene was highly successful, with greater than 95% conversion achieved using a single equivalent of nitric acid and a catalytic quantity (10 mol%) of ytterbium triflate. The real benefit of this work was that the only side-product was water, and that the catalyst could be recovered and reused—most unusual for a Lewis acid.EPSRC and Air Products sponsored further work in the area aimed at scoping the reaction and studying the mechanism. On screening the entire series of lanthanide( III) triflates for catalytic activity (for nitration) it became evident that there was a clear relationship between the extent of nitration and the ionic radius of the lanthanide ion with activity increasing as the radius decreased.This led Barrett and Braddock to postulate that the everincreasing electrostatic interaction between the lanthanide ion, and nitric acid was responsible for the increase in activity. Further mechanistic study led to the belief that nitric acid was displacing water in the inner co-ordination sphere of the lanthanide ion, this resulted in the reversible elimination of a proton, as shown.It is this proton that leads to the accentuation of the Brønsted acidity of the nitric acid through formation of a nitronium ion. [Ln(OH2)9]3+ï[Ln(OH2)y(HNO3)]3+ [Ln(OH2)y(HNO3)]3+ï[Ln(OH2)y(NO3)]2+ + H+ H+ + HNO3ï NO2 + + H2O Although this work has not yet been commercialised, Professor Barrett is currently patenting extensions to this technology for which he sees many commercial applications.The rare earth metals are not actually that rare and neither availability nor cost would preclude their use as commercial catalysts. With the current system the recycling technology is different to that available on most industrial plants, Barrett believes however that new plants, designed to use lanthanide catalysts, would be cost effective.A significant advantage for industry would be heterogeneous versions of the catalyst which may be just around the corner. Professor Anthony Barrett In the first of a new series of reports looking at some of the leading workers in the field of green chemistry and clean technology, Mike Lancaster describes some of the work of Tony Barrett’s group at Imperial College of Science, Technology and Medicine, London.‘Barrett believes that new plants, designed to use lanthanide catalysts, would be cost effective’ Tony Barrett’s group at Imperial College of Science, Technology and Medicine TG98 Green Chemistry August 1999 C G F OC U S O N. . . Barrett is a keen supporter of the atom economy concept but at the end of the day chemical instinct is usually a good measure.In terms of chemistry education Tony Barrett is a traditionalist, he firmly believes in teaching fundamental core chemistry and that undergraduate courses should not be modified too much to include latest green chemistry methodology. If he could revolutionise one area of chemistry with clean technology Barrett would choose aromatic transformations —which are at the centre of the fine and speciality chemicals industry.Meanwhile as Chris Braddock starts on an independent career in the area of clean technology he is looking to use metal free asymmetric catalysts (MFAC) such as recyclable carbocations to overcome the problematic issue of toxic metal residues in pharmaceutical products. I’m sure we will be hearing much more about MFAC in the coming few years. Further Reading A.G. M Barrett and D. C. Braddock, Chem. Commun, 1997, 351. S. Kobayashi and I Hachiya, J. Org. Chem., 1994, 59, 3590. B. M. Trost, Angew. Chem., Int. Ed. Engl., 1995, 34, 259. F. J. Walker, A. G. M. Barrett, D. C. Braddock and D. Ramprasad, Chem. Commun., 1997, 613. F. J.Walker, A. G. M. Barrett, D. C. Braddock, R. M. McKinnell and D. Ramprasad, J. Chem. Soc., Perkin Trans. 1, 1999, 867. Esterification with lanthanide(III) triflates Esterification is another reaction that finds widespread use in the chemical industry. At first sight this is green chemistry at its best, the only by-product being water, for example: ROH + AcOH ® ROAc + H2O Chemistry is rarely that simple however; the reaction is reversible and typically a significant excess of either acid or alcohol as well as a strong mineral acid are required to drive the reaction forward.Azeotropic removal of water also drives the reaction but this sometimes requires complex and expensive distillation towers and produces significant amounts of acid waste. Although Lewis acids do catalyse the reaction they offer no benefit in terms of clean technology.Since the lanthanide triflates are stable in water they seemed an obvious choice to Barrett and Braddock. They found that both scandium (III) and lanthanide(III) triflates catalysed the acylation of a range of primary, secondary and tertiary alcohols with acetic acid. Quantitative yields were obtained with primary alcohols such as phenethyl alcohol at room temperature using just 5 mol% Sc(OTf)3, and even the extremely bulky tertiary alcohol 1-adamantanol could be acetylated to 80% conversion within minutes at reflux.The Green Chemistry Movement Within the UK Tony Barrett believes that one of the most important factors in pushing forward clean technology was the establishing of the Institute of Applied Catalysis (iAc) which came out of the Government’s Foresight panel of which he was a member. iAc has been responsible for encouraging and supporting catalyst research in the UK that is at the heart of much clean technology.Indeed Barrett believes more money should be put into the iAc programmes to underpin clean technology themes. One weakness of the current funding programme in the UK is that it is not always related to the needs of society, programmes often being funded for political rather than social need.Two of the most important aspects, in Barrett’s view, to drive new clean technology into industry are the forging of close links between academia and industry at an early stage and the establishment of close working relationships between chemists and chemical engineers so that the process is developed alongside the chemistry.To this end Barrett and Braddock are currently working on establishing a MSci course in ‘Chemistry with Fine Chemicals Processing’ in conjunction with the Department of Chemical Engineering at Imperial. Professor Barrett also attributes much of the success of his long collaboration with Air Products to the significant involvement of engineers. Imperial saw the need to involve industry at an early stage in academic research several years ago.A full-time post, the Director of Strategic Alliances, was created to enable the research work to be marketed and to identify potential industrial partners. This has been of invaluable help to the work of the Barrett group.At the end of the day the key drivers which Barrett thinks will force industry to become more green are financial and legislative. He is starting to see both of these come together in the pharmaceutical industry. There is now much more competition in this area forcing prices down and as the cost of waste rises so new technology is needed. As outsourcing becomes widespread so does the opportunity for new, competitive clean technology. Barrett is however scathing of people and technology jumping on the green bandwagon. As an example he cites biotransformations, generally perceived as being green, but many examples suffer from extremely low turnovers producing huge volumes of waste. One problem we have is defining what ‘green’ is, especially when comparing processes. Professor ‘the key drivers which Barrett thinks will force industry to become more green are financial and legislative’ ‘Barrett believes that clean technology in the UK was pushed forward by the establishing of the Institute of Applied Catalysis’ ‘Barrett would like to see aromatic transformations revolutionised with clean technology’ Visit the Green Chemistry homepage FREE electronic access to full contents of Issue 1 http://www.rsc.org/greenchem

ISSN:1463-9262    

DOI:10.1039/a906797c

出版商:RSC    

年代:1999

数据来源: RSC

摘要:

Green Chemistry August 1999 G99 Constitution and membership The Forum is constituted with an Executive Committee and an Activities Committee, both supported by a Secretariat based at the Institution of Civil Engineers. Membership of both committees is not limited to Engineers, but is by invitation only, with the minimum requirements of chartered status in their own field, and formal approval of the Executive.Stuart Luxon was the RSC-Environment, Health and Safety representative on the Forum until he resigned from the EHSC a few years ago. I was nominated as his successor (partly due to my background as Chief Chemist and Company Environmental Health Chemist with Rolls-Royce plc.), then was invited to join the Activities Committee the following year. When Darrol Stinton, a former testpilot, and now Engineering consultant in Aero and Marine, stepped down from the chairmanship due to overseas commitments in December 1998, I was offered and accepted the chair.Following the resignation of Professor Bennett, also due to overseas commitments, Stuart Mustow, a distinguished Fellow of the Royal Academy of Engineering, accepted the Executive Chairmanship in January 1999.F OR U M The Hazards Forum Both committees have a balanced representation from engineering, science, technology, safety and emergency planning. Recent issues addressed by The Hazards Forum Seminars and meetings have included: l The Successful Management of Safety l Safety of Ships l Flood Hazards in Bangladesh l An Engineer’s Response and Tasks in Disaster Preparedness l Blowing the Whistle for Safety l Risks to the Public–The Rules, The Rulers and The Ruled l Gas-Rich Volcanic Lakes– A Major Natural Hazard Strategy for the Future The Forum was initially conceived to ensure that lessons of the past learned from major disasters both natural and man-made should not be forgotten.It has been recognized that with its multidisciplinary composition, the Forum is ideally suited to address the whole spectrum of issues of Hazard and Risk.In order to address this spectrum however, a much greater degree of cooperation will be sought with other Institutions and major companies in organizing attractive meetings that will offer a balanced perspective. The British National Committee for the UN International Decade for Natural Disaster Reduction (IDNDR) is established under the auspices of the Royal Society and the Royal Academy of Engineering to co-ordinate British initiatives in support of the decade.It is interdisciplinary and reflects the involvement of many British nationals; consultancies and NGOs in natural disaster-related work worldwide. The decade ends in December 1999 and the Committee will be disbanded, but there is an opportunity for the Hazards Forum to provide an on-going focus for the work and in particular to incorporate consideration of risks arising from British natural hazards.The next seminar will be a half-day C G Terry Farthing describes an interdisciplinary forum for engineers concerned with the mitigation of both natural and man-made disasters Historical perspective The Hazards Forum, a registered Charity, was founded in 1989 by the Institutions of Chemical, Civil, Electrical and Mechanical Engineers to provide an interdisciplinary focus for: l the study of disasters and the promulgation of lessons drawn from them l the promotion of risk reduction strategies l raising awareness in the professional community of the responsibility of the individual to improve safety Disasters arising from both natural and man-made hazards were within the remit although it was British examples of the latter that were the primary drivers for the initiative by the Institutions.The first Mission Statement stated ‘The Hazards Forum exists to provide a focal point in which engineering features in the mitigation and reduction of both manmade and natural hazards and disasters’.Forum membership was initially restricted to the engineering institutions and associated bodies but in recent years membership has been extended beyond engineering. Other institutions and societies, including the Royal Society of Chemistry, the Geological Society, the Institute of Physics, Institute of Occupational Safety and Health, Institute of Hydrology, are Associate Members.A range of companies, distinguished persons and others with an interest in hazards and risk are also included in the membership. The Forum, under the successive Executive chairmanship of Sir Frederick Warner, Sir Bernard Crossland and Professor Phillip Bennett, has pursued its aims and objectives via regular meetings, special keynote events and the publication of a Newsletter and books.The aim has been to provide a service to members and to bring important issues to a wider audience. ‘The Forum exists as a focal point for engineers involved in mitigating hazards and disasters’G100 Green Chemistry August 1999 one with the title, The Montreal Protocol–Twelve Years On. Chaired by Sir John Krebs, Chief Executive of the National Environmental Research Council, with speakers from The Meteorological Office, Rolls-Royce plc, ICI, Environmental Investigation Agency and the Health and Safety Executive (see details in box).Responsible Care Chemical Industries Association Re-launch Responsible Care Responsible Care is the Chemical Industries Association (CIA) commitment to continual improvement in health, safety and environmental performance and openness in communication about its activities.The CIA organised a meeting in May 1999 to both celebrate 10 years of commitment to Responsible Care and take a critical look at what is needed for the next 10 years. The highlight of the day was a speech by Michael Meacher—UK Minister of State for the Environment. Mr Meacher announced that a New Chemicals Strategy would be launched within the next few months.It is likely that this will contain measures to ensure that industry pursues a more sustainable approach in the production and use of chemicals. The strategy is also likely to emphasise the requirement for improved information on the environmental risk of all chemicals with the likely phase out of the most toxic and persistent chemicals.Mr Meacher did however make it clear that industry competitiveness will be maintained. Although somewhat critical of the current state of the Responsible Care programme, he did offer some praise for what had been achieved; it was clear however that he expected industry to become much more open and pro-active in obtaining SHE (safety, health & environmental) information and making this available to the public.Meacher also announced that his department had commissioned a full life cycle assessment and economic analysis of PVC and alternatives to it (such as wood for window frames). The work will be carried out by ENTEC and Ecobalance UK and will take a year to complete. The theme of improved openness F O R U M C G The Montreal Protocol... 12 years on Half-Day Seminar on October 13 1999, at the Institution of Civil Engineers, 1 Great George Street, London, UK In 1987, the developed nations signed an agreement in Montreal, Canada to limit production of, and ultimately ban the general production and use of Halons, chlorofluorocarbons [CFCs], carbon tetrachloride, and certain other solvents which had been shown to have a damaging effect upon the Global Ozone Layer.This agreement, to which some 130 nations are now committed, was termed the MONTREAL PROTOCOL. The Seminar has been arranged to hear the extent to which the Protocol has been successful in damage limitation in respect of the Ozone Layer, the lessons learnt by industry, the current availability of alternative substances and the problems experienced in identifying CFC smuggling from countries which are not signatories to the protocol. Chairman: SIR JOHN KREBS, currently Chief Executive of the National Environmental Research Council.Presenters: JOHN AUSTIN (The Meteorological Office), IAN LIDDLE (Rolls-Royce plc), MICHAEL WALKER (ICI), STEVE TRENT (The Environmental Investigation Agency), BERNARD ROBINSON (The Health and Safety Executive). Tickets (£56 for Members of the Hazards Forum and Affiliates; £70 for Non-Members) are available from The Hazards Forum Secretariat, 1 Great George Street, London SW1P 3AA Tel. 0171 665 2158, Fax 0171 233 1806, E-mail torey_d@ice.org.uk) on both product and process information recurred several times throughout the day. It was particularly encouraging to hear this message coming from Paula Gough (CIA Young Person of the Year) who was speaking on behalf of younger chemists and engineers in the industry.She believed that industry must accept, indeed encourage, greater transparency of data. At the same time industry should produce cost benefit analysis studies to show that being eco-friendly can also have a positive effect on the bottom line.There were also several speakers calling for industry to accept benchmarking, sharing of best practice and independent auditing in all areas of responsible care. These calls were particularly strong from the Environment Agency and the Health and Safety Executive. CIA members recognised these areas of concern and were selfcritical over the industry’s obsessive concern for confidentiality.With over 150 senior managers attending the event, we will hopefully see industry taking notice of these concerns. Responsible Care is now an undoubted success story but took a long time to gain acceptance since its launch in Canada in 1986. As a direct result of the programme CIA members have made significant improvements to both toxic release and energy efficiency through process development and uses of alternative materials.The histogram below shows the improvements made in release of red list substances (now only 20 tonnes per annum) and energy efficiency since the CIA’s launch 10 years ago. In re-launching the programme Dr Joe Blaker, CIA President, highlighted two important new statements that CEOs of member companies will be required to sign up to.l ‘We will work to conserve resources and reduce waste in all our activities’ l ‘In addition to ensuring our activitiesGreen Chemistry August 1999 G101 meet relevant statutory obligations, we will share experience with our industry colleagues and seek to learn from and incorporate best practice into our own activities’ Industry is taking steps to become greener and cleaner; the conference achieved an appropriate balance of self-congratulation, critical assessment and suggestions for improvement. This is indeed good news for green chemists in all walks of life.European Responsible Care questionnaire A questionnaire was sent to member companies of CEFIC (European Chemical Industry Council) which aimed to illustrate how Responsible Care is being implemented in Europe.Those responding to this questionnaire also had the opportunity to submit a case history which demonstrated some aspect of Responsible Care implementation. For example, Celanese has opened a 100000 tonnes/y butyraldehyde facility based on unique high-pressure rhodium technology, which enables improved use of raw materials and has lower production costs.The new process is more environmentally acceptable than the previous cobalt-based technology because it uses less energy and no waste water accumulates. Complete conversion of raw materials results in a considerable reduction in the number of side products generated. Other companies providing case studies include Borealis, BP Amoco, Henkel, Lyondell, and Shell Chemicals.Sweden implements OSPAR policy Sweden has become the first country to implement the policy set out at last year’s meeting of the OSPAR Commission1 at which North Atlantic nations agreed to eliminate emissions of hazardous chemicals that accumulate in biological systems or are environmentally persistent, as well as carcinogens and hormone disrupters. It had been thought that the Swedish policy would be even tougher after an Environment Ministry report recommended immediate prohibition. 1 The OSPAR Commission came into force on 25 March 1998, replacing the OSlo and PARis Conventions. For further information see http://www.ospar.org/eng/html/welcome.html F OR U M C G growing membership and requests for information. Our web site is now up and running (http://www.chemsoc.org/gcn); we will be continuously improving and updating this.Additional programming is required before the members’ area goes live but this should be available within a few weeks. Please send us any ideas or materials for inclusion. We recently held the first meeting of the Technical Advisory Panel; consisting of representatives of government departments, regulatory authorities, trade associations, research funding bodies and professional associations (see web site for full list of members).Topics discussed included the best ways of providing educational material for schools and universities and how best to involve industry in technology transfer and sharing of best practice. We are going to establish sub-panels on education and industry to work out the details of how to move forward—if anyone wishes to be involved please let us know.The official launch of the GCN will be held at the British Association Festival of Science Week on 16 September in Sheffield. We are still working out the full details of the event but if anyone would like to attend please let us know. Also in September (28th) we will be holding our first Green Chemistry seminar in York.The aim of the one-day seminar is to get young people discussing their work and to learn about the wider aspects of Green Chemistry outside their immediate research area; as such the majority of speakers will be postdocs from ‘local’ universities. We are fortunate in getting Ken Seddon from Belfast to give the Keynote lecture on ionic liquids, one of the fields that offer so much promise for future Green processes.Please let us know if you would like to attend. Still on the conference theme a note for your diaries; for April 2001, we are starting to plan the first RSC Green Chemistry conference to be held in Swansea. All aspects of Green Chemistry will be covered but we will be again be focussing on the work of younger chemists and engineers as well as highlighting what is happening in industry.Mike Lancaster, GCN Manager (greennet@york.ac.uk) 1999 Queen’s Awards The 1999 Queen’s Awards included 5 awards for technological achievement. Among those honoured were Zeneca Metal Extraction Products in Manchester for a novel magnesium-based process to manufacture a chemical for extracting copper from waste ore.There is a corresponding reduction in effluent from the process of some 85%. Synetix in Billingham won an award for the Hydecat process which is a fixed-bed catalytic process for the treatment of waste sodium hypochlorite liquor which is created whenever chlorine is produced or used. The hypochlorite is converted into oxygen and salt solution. Sustainable Technologies Initiative A new Sustainable Technologies Initiative (STI) has a total of £7.8m over 3 years available in funding to help businesses reduce their impact on the environment.The funding will support the development of technologies to help businesses produce less waste and pollution, use resources more efficiently and achieve greater social equity in their operations and products. Details of the initiative are still being finalised but it is likely that it will act as an umbrella for a range of activities focussed largely on R&D programmes and projects. The common theme of these will be the integration of sustainability into processes and products from the design stage. Sectoral and cross-sectoral topics will be addressed. It may be possible for some of the funding to be used to support small projects to investigate scope for creating a stimulated interest in sustainable technologies. Further information is available from the Department of Trade and Industry in London (tel. 0171 215 2988). Royal Society of Chemistry Green Chemistry Network The GCN has now been active for around 6 months. During this time we have published a number of general articles promoting the Green Chemistry movement; these have been met with a great deal of interest and resulted in invitations to give various presentations. This snowballing effect has resulted in

ISSN:1463-9262    

DOI:10.1039/a906798a

出版商:RSC    

年代:1999

数据来源: RSC

摘要:

Introduction In 1997, Greenpeace opened up a new front in its campaign against polyvinyl chloride (PVC), raising concerns about the safety of phthalate esters in children’s toys. Despite the defeat—by one vote—in the European Commission of a measure to ban phthalates in certain children’s toys in 1998, many toy retailers and manufacturers are eliminating phthalates and PVC from their products. Although eclipsed by media coverage of genetically modified foods, the debate over phthalates in toys has all the hallmarks of a classic scientific controversy: conflicting accounts of scientific ‘facts’ fought out in public by a plethora of experts.Superficially about science, most controversies are less concerned with scientific facts and more about politics and the democracy of decision-making.The current phthalate controversy in Europe began in Denmark. In April 1997 Danish authorities approached the European Commission with concerns about the levels of phthalates being released from teething rings made in China for a company called Chicco- Artsana. Although the manufacturer withdrew the products from sale in Europe, the issue revealed the absence of a validated method for testing phthalate migration.As a result—and in response to lobbying by Greenpeace and the toy industry—the Commission asked its Scientific Committee on Toxicity, Ecotoxicity and the Environment (CSTEE) to evaluate the evidence. CSTEE evaluation The CSTEE met five times during 1998, examining the amount of phthalate esters in toys, data on leaching from toys, exposure to phthalates from other sources as well as their toxicity.In its review of the literature, the CSTEE found that DEHP causes liver cancer in rats and mice, but via a pathway that is less relevant in humans. It also noted that DEHP caused reproductive effects, including testicular atrophy, embryo toxicity and teratogenicity. Other phthalate esters produce a similar pattern of effects, and there is some evidence that BBP has oestrogenic effects in vitro.1 In April 1998 the CSTEE concluded that for two phthalate esters—DINP and DEHP—estimated safety margins were below 100, and the safety margin of 8.8 for DINP ‘gave cause for concern’.However, when the CSTEE met again in November 1998, results were available from Dutch and Austrian tests on the release of DINP and DEHP into saliva in human volunteers, plus results from tests by the US Consumer Product Safety Commission (CPSC) laboratory.These data gave a more reassuring picture of the amount of phthalates leached from toys when sucked, but the CSTEE said: ‘The revised margin of safety (MOS) values are 75 for DINP and 19 for DEHP, respectively. The MOS for DINP raises some concern as it is less than the previously recommended safety margin of at least 100.The MOS for DEHP raises clear concern.’2 Its November 1998 opinion concluded: ‘The CSTEE recommends that an interlaboratory comparison exercise be carried out in order to document the reproducibility of Phthalate esters in children’s toys— calls for product substitution Becky Allen examines a current public safety controversy Phthalate esters Phthalate esters have been widely used since the 1940s, especially as plasticisers in vinyl products to make them soft and flexible.Examples include the following: l butyl benzyl phthalate (BBP) l diisononyl phthalate (DINP) l dibutyl phthalate (DBP) l di-2-ethyl hexyl phthalate (DEHP) l di-n-octyl phthalate (DNOP) l diiso-decyl phthalate (DIDP) The phthalate esters causing the most concern as regards toxicity are DEHP and DINP.Baby chewing PVC teething ring containing phthalates F EAT U R E C G G102 Green Chemistry August 1999Green Chemistry August 1999 G103 F E AT U R E C G could attempt to make phthalates in PVC more immobile, switch to plasticisers other than phthalate esters, or replace PVC altogether.Although recent Indian work suggests that surface-modification techniques using sodium sulfide might prevent phthalate migration,3 previous attempts to lock phthalates into PVC have resulted in loss of flexibility. Alternative plasticisers include adipates and citrates, although less is known about their toxicity and mobility in PVC. The third option is replacing PVC with other materials such as polyolefins.Metallocene polyolefins, thermoplastic elastomers and ethylene vinyl acetate are identified as interim substitutes for PVC in toys in a report commissioned from the University of Massachusetts by Greenpeace.4 But despite being safer and cost-competitive, industry currently lacks the will to change, the report says. ‘Rather than spending resources on only assessing the risks of phthalate plasticiser in PVC toys, attention should focus on which alternatives can be developed and selected to replace PVC in toys,’ says the report.It also points to new technologies such as thin wall injection moulding and gas assisted injection moulding as a way forward. However, in the long term the report says the toy industry should abandon plastics based on petrochemicals altogether.The report concludes: ‘Advancements in biodegradable plastics hold hope for the future production of toys that are more sustainable through their life cycle.’ Recent developments Dutch migration test validated5 On 31 May 1999 it was announced that the so-called ‘Dutch Migration Test’, which can be used to measure the the Dutch laboratory method to measure phthalate release from PVC toys.Studies performed in order to shed light on the issue of buccal absorption of phthalates should be carried out. The CSTEE further recommends that additional studies be carried out in order gain more insight as to the total time children are mouthing PVC toys.’ Calls for a ban Despite the narrow defeat in the European Commission of measures to ban phthalates in toys in 1998, several member states—as well as toy manufacturers and retailers—have taken action, and in December 1998 the US CPSC asked industry to find substitutes for phthalates in products for children under three.Although not recommending a ban, the CPSC said there were ‘several areas of uncertainty where additional scientific research is needed’.As a precaution while more scientific work is done, the CPSC requested industry to remove phthalates from soft rattles and teethers. By early 1999, companies including Hasbro, Mattel and Toys-R-Us stopped using phthalates in teethers and rattles or removed phthalate-containing products from their shelves. Although Greenpeace has presented such moves as another victory in its war against PVC, industry bodies including the US Chemical Manufacturers’ Association (CMA) Phthalate Esters Panel say that adverse effects in animals exposed to phthalates only occur at ‘extremely high doses’ and that DEHP, about which the CSTEE expressed most concern, is rarely used in children’s toys.‘Countries that are banning phthalates are not acting in accordance with the scientific evidence,’ says the CMA.Product substitution Amid the heat and light of the debate over phthalate toxicity, less is being said about alternatives to phthalates in PVC, or alternatives to PVC itself in children’s toys. According to Maurits Bruggink of the Toy Industries of Europe: ‘An unfortunate consequence has been the announcement by some companies that they will use alternative raw materials, not because their products are unsafe but simply because of pressure.In the end it will be the consumer who will suffer, not only from lack of choice, but also because many raw materials are far less well understood.’ Manufacturers that decide to address consumer concerns about the safety of phthalates have several choices. They Phthalates on the Web For further information on phthalates, especially in PVC toys, see the following websites: l http://www.greenpeace.org/ -comms/pvctoys/ l http://www.vinyltoys.com l http://www.phthalates.com l http://www.vinylinfor.org l http://www.ecpi.org and links therefrom.Soft plastic toys often end up in children’s mouths ‘A Greenpeace report concludes that the toy industry should abandon plastics based on petrochemicals’US panel confirms safety of phthalates6 An independent expert panel convened by the American Council on Science and Health (ACSH) announced on 22 June its conclusion that phthalates are safe for use in toys and medical devices.The 17-member panel, chaired by the former US Surgeon General Dr C. Everett Koop, reviewed a wide variety of published and unpublished scientific literature from the US, Canada and Europe to evaluate potential health risks from DEHP and DINP.The conclusions were that DEHP and DINP are not carcinogenic nor do they have other harmful effects at levels to which people are exposed, casting doubt on the extrapolations which have been made in the past from animal studies to human health. On toys, the panel recommends further studies to expand knowledge of children’s exposure, but states clearly its view that ‘DNIP in toys is not harmful for children who use these toys normally.’ The controversy goes on The conclusions of the ACSH report have been welcomed by the European Council for Plasticisers and Intermediates.But Greenpeace and other organisations do not accept the panel’s findings and claim that there is sufficient doubt about the risks involved to ban the controversial materials.They will therefore continue their campaign to ban PVC and phthalates. G104 Green Chemistry August 1999 F E AT U R E C G migration of the phthalate plasticiser DNIP from toys etc. has been successfully validated in trials organised by the TNO Nutrition and Food Research Institute in the Netherlands, and carried out in 6 laboratories in Germany, the Netherlands and the UK; it was expected that the test could be also validated for other phthalates.The test could be used to ensure that toys and childcare items, intended to be put in the mouths of children under 3 years old, conform to the migration limits suggested by CSTEE. Whether EU Member States, including the Netherlands, adopt the Dutch test method still has to be decided. Any EU-wide agreement may have to follow collaborative trials being conducted by the EU Joint Research Centre (JRC) at Ispra in Italy.The JRC is believed to be looking at a number of methods, including one similar to that of the Dutch that has been developed by the Laboratory of the Government Chemist in the UK and which is also currently undergoing interlaboratory testing.Danish regulation of phthalates On the 1 April 1999 the Danish ban on phthalates in toys and baby articles for children under 3 years of age came into force, making it the second European country to enforce such a ban, following Austria which banned them in January 1999. In June 1999 the Danish Government announced a new plan to regulate the use of PVC and phthalates by introducing taxes on both of them—2 Danish Kroner per kg of PVC and 7 Danish Kroner per kg phthalates. In addition the Danish plan covers a range of initiatives which, if fully implemented, would keep PVC away from incineration plants.In recent years Denmark has taken the lead in the regulation of PVC and phthalates, and has found that voluntary agreements between its government and the PVC industry have not worked—hence the proposed legislation.The Danish goal is to reduce the use of phthalates by 50% by the year 2010. ‘A US panel states that DNIP in toys is not harmful for children who use these toys normally’ ‘The Danish goal is to reduce the use of phthalates by 50% by the year 2010’ References 1 CSTEE (1998). Opinion expressed at the CSTEE third plenary meeting, Brussels, 24 April 1998. 2 CSTEE (1998). Opinion expressed at the CSTEE third plenary meeting, Brussels, 26–27 November 1998. 3 A. Jayakrishnan and S. Lakshmi. Immobile plasticiser in flexible PVC. in Nature, 17 December 1998, 396, 638. 4 University of Massachusetts/ Greenpeace (1999). A review of the availability of plastic substitutes for soft PVC in toys. 5 For information on the Dutch Migration Test see http://www.ecpi.org/pressreleases/ pr990531.htm 6 For information on the ACSH Panel findings see http://www.acsh.org

ISSN:1463-9262    

DOI:10.1039/a906799j

出版商:RSC    

年代:1999

数据来源: RSC

摘要:

C G Green Chemistry August 1999 G105 F E AT U R E ead usually enters the environment by one of four routes—primary or secondary smelting, fabrication processes or paint manufacture, disposal or discarding of unwanted lead-containing materials and combustion of coal and other fuels, especially leaded gasoline. Lead emission from industrial processing is subject to stringent regulation of acceptable emission levels and safe working practice and industrial emission is usually centred on a specific locality and so largely confined to relatively small geographical regions.Lead from automobile exhaust In the mid-1980s approximately 85% of all lead discharged into the atmosphere originated from automobile exhaust.1 Alkyl lead compounds, especially tetramethyl and tetraethyl lead, have been accepted as antiknock agents in gasoline since tetraethyl lead was recognised as an effective antiknock agent in 1921.2 The environmental health implications of lead in the atmosphere were brought into question3 as early as 1922 but, from 1923, when it first went on sale, consumption of leaded fuel soared.A low-level background concentration of lead, arising through mobilisation from lead ores, is naturally present in the environment but anthropogenic lead emission has raised atmospheric lead levels significantly since leaded fuel became widely used.Comparison of the Northern Hemisphere air lead levels with those of the Southern Hemisphere (where there is a substantially lower anthropogenic contribution) shows that the Northern Hemisphere has up to 10 times as much airborne lead as the Southern—0.05–0.20 µg Pb m–3 compared with 0.02 µg m–3.The natural atmospheric concentration of lead arising through airborne particulates and gaseous diffusion should, it is calculated,4 be as low as 5 3 10–4 µg m–3. The mean lead concentration in the earth’s crust is just 16 ppm5 and it has been estimated that, in prehistory, the airborne concentration was 4 3 10–4 µg m–3 .In North America in the mid 1980s levels in even the most remote areas were around 10 3 10–4 µg m–3 and up to 10 µg m–3 in urban areas. Although substantially higher than natural background levels this represented a decrease from the levels of the 1960s and 1970s when leaded gasoline consumption was higher. In 1967, atmospheric lead levels in large US cities averaged 10–35 µg m–3—an isolated case of ca. 70 µg m –3 was measured near Hollywood, California.6 In dust collected in Birmingham, England from 1972–75 lead was found at a concentration of ca. 970 ppm.7 The particle size strongly influences environmental lead burdens—the smallest particles contain the greatest lead concentrations. The physiological effects of lead pollution are well documented. An atmospheric lead concentration of 1 µg m–3 can produce a rise of 1.0 µg 100 cm–3 in blood and a lead concentration in the soil of 1000 ppm results in 0.6 µg 100 cm–3 increase.8 The ‘natural’ average lead content4 is 0.25 µg 100 cm–3 and the Lead at the roadside Kam Kit Lam, Gerry Ottewill, Brian Plunkett and Frank Walsh at the University of Portsmouth describe the change to roadside vegetation in southern England resulting from the switch from leaded to unleaded fuel * L *The authors gratefully acknowledge Hampshire Wildlife Trust for their permission to sample on land under their management.F E AT U R E C G G106 Green Chemistry August 1999 distances of 0 m and 80 m, respectively, from the roadside.Lead content in washed samples averaged 55% of that in the unwashed, ranging from 2.31 (±0.38) to 16.8 (±0.1) µg Pb g–1 at 0 m and 80 m distances, respectively.The distance profiles for washed and unwashed samples ‘acceptable’ blood lead level,8 70–80 µg 100 cm–3 in adults. For children1 25 µg 100 cm–3 is considered the upper limit ‘normal’. Over the period 1976–1980, as use of leaded fuel fell, mean blood levels began to decrease.5 Consumption of leaded gasoline began to decline only when legislation was passed in the US enforcing the reduction of exhaust emissions—50 years after we started to use it! The capital cost to the US refineries to produce 100% lead free petrol was almost 15 000 million U.S.dollars,9 but by 1985, unleaded fuel had the major market share, 78% of the total compared with only 25% in 1977.We have looked at lead distribution on the vegetation alongside a length of the A27 major roadway in three different years, 1978, 1984 and 1994, measuring the lead concentrations and examining their variation over time, distance from the road and vegetation type.† Lead in grass samples Figure 1 shows the lead content of grass samples as a function of distance from the roadside.The lead content in unwashed grass samples collected in 1978 is shown in Figure 1(a). It ranged from 77 µg Pb g–1 to 45 µg Pb g–1 at distances of 37 m and 50 m, respectively, with distinct maxima and minima at distances of approximately 20 and 50 m. The distance profile for the 1984 samples [Figure 1(b)] shows a more linear pattern falling from 160 µg Pb g–1 at 10 m to 15 µg Pb g–1 at a distance of 60 m.Results for the 1994 analyses, illustrated in Figure 1(c) are reported for both washed and unwashed samples. The lead in unwashed grass had a concentration range from 5.22 (±1.05) µg Pb g–1 to 35.0 (±0.9) µg Pb g–1 at both fall from a maximum at the road edge to a shallow minimum at 20 m. A second maximum occurs at about 40 m where the concentration is almost as high as at the roadside.From 40 m to 80 m overall the lead content drops. The unwashed sample profile has a much Figure 1. Lead content of grass samples as a function of distance from the side of the A27 roadway: (a) 1978 data; (b) 1984 data; (c) 1994 data. † The sampling sites lay beside a busy section of the A27 trunk road running through the Farlington Marshes Nature Reserve, Hampshire, England.A series of posts, 1.5 m in height, was erected in a line perpendicular to the carriageway. The posts were placed at 10 m intervals up to a total distance of 90 m from the roadside. Vegetation samples consisted of grass, weed and moss. The species of grass were, primarily, False-brome (Brachypodium sylvaticum), foxtail (Alopecurus geniculatus) and Yorkshire fog (Holcus lanatus).Weed samples were silverweed (Potentilla anserina); the moss was Sphagnum acubifolium aggregate.10 All samples were air-dried and then oven-dried for 36 h at 110 ºC. The dried material was ground into a powder and portions of the powdered vegetation (0.5–1.5 g) were digested for 2 h in a 4:1 v/v mixture of aqueous Analar nitric and perchloric acids (25 cm3).The digest was filtered and diluted twofold using 1% nitric acid. Samples were analysed, in triplicate, using flame atomic absorption spectroscopy. The lower detection limit was 0.02 µg Pb cm–3 with a concentration range linear up to 20 µg Pb cm–3 .Green Chemistry August 1999 G107 C G F E AT U R E shallower maxima and minima, particularly evident around 40 m.The decrease in the lead content at 40 m is around 70% with washing. At 60 m the reduction due to washing is much less— only about 2%. Lead in silverweed samples Figure 2 shows distance profiles for washed and unwashed samples of silverweed collected in 1994. Concentrations ranged from 1.7 (±1.1) µg Pb g–1 at a 20 m distance to 6.4 (±2.0) µg Pb g–1 at 80 m in unwashed silverweed and from 0.83 (±0.21) µg Pb g–1 to 4.7 (±1.3) µg Pb g–1 at corresponding distances in washed silverweed samples.As for grass, washing produced a reduction in lead content but a much smaller reduction than in the silverweed. Washed samples of silver weed were found to contain approximately 70% of the lead content of unwashed ones, a higher percentage than the 55% that remained in the washed grass samples.Washing, which removes particulate lead effectively, appears to have a much greater effect on grass than on silverweed. A multiple t test (8 degrees of freedom; 95% confidence level) confirms a statistically significant difference in lead content between washed and unwashed samples of grass (texpt = 7.96; tcrit = 2.31).A similar statistical test (7 degrees of freedom; 95% confidence level), on results from silverweed samples, indicates no statistically significant difference between washed and unwashed specimens (texpt = 0.68; tcrit = 2.37). Profiles for washed and unwashed samples follow similar overall shapes falling from a maximum at the roadside to an overall minimum at ca. 80 m. Within this, a smaller maximum appears at 40 m.As for grass samples, the greatest difference between washed and unwashed sample lead content (2.1 µg Pb g–1, 39%) occurs at 40 m. At a distance of 70 m from the road no difference at all is discernible. At the sampling site hedgerows lined the roadside. The shelter provided by these explains the reduction in grass lead content that occurs in the initial 20 m from the road.Interestingly, the drop in weed lead concentration is delayed, occurring between 20 and 30 m, probably due to shielding by higher grasses in the open field. The maxima at around 40 m are due to the dispersion pattern of automobile exhaust. Sunlight and traffic heat the air immediately above the road surface. The warmed air rises carrying automobile exhaust emission which is dispersed along a line between the vertical and horizontal planes.Thermal currents, wind speed and direction also influence the dispersion and the fact that the road here is approximately 5 m above the surrounding field is probably a contributory factor. The degree of lead removal is closely related to the surface texture of the leaves. A rougher surface, such as that of the silverweed, can retain particulate material better than the smooth surface of the blades of grass and the rougher leaf holds the deposited material more tenaciously when washed.The relationship we observed between lead retention and leaf texture agrees with results found by other authors.11 It was shown,11 using radioactively labelled petrol, that rough or hairy leaves such as white poplar retain up to 8 times as much lead as smooth ones like laurel.Hazel, oak, birch and ash trees were examined at distances up to 50 m from the edge of the M25. The lead concentration decreased exponentially for hairy, retentive hazel leaves but smoother oak leaves had lower surface lead levels that varied differently with distance. Leaves closest to the motorway showed lower levels than those more remote, possibly due to exposure to the adverse weather as Figure 2.Lead content of weed samples as a function of distance from the side of the A27 roadway (1994 data).well as to their lower retentive capacity. Our results indicate that, on average, the grass at a given distance from the road has a greater deposited lead content than silverweed at an equivalent distance.The relative concentrations in grass and silverweed result from a combination of two conflicting effects, surface texture and duration of exposure to exhaust emission. The rougher texture of the silverweed leaf allows adhesion of particulates and so tends to raise the lead levels in silverweed relative to those in grass, but the grass is present throughout the year. Its persistent exposure to the automobile emissions compared with the seasonal exposure of the silverweed results, overall, in accumulation of more lead particulates, i.e.the length of exposure outweighs the differences due to surface roughness. The balance of these two effects needs close monitoring, allowing for seasonal trends in automobile use and emission dispersion and seasonal plant growth patterns with analysis of foliage at different stages of development. The age of foliage influences the degree of metal retention.12,13 Marked seasonal variation in retained lead has been observed,14 with a maximum in autumn when leaves have been exposed for the longest time.The longer exposure clearly outweighs the growth dilution effect.Other factors also influence lead uptake by vegetation. Different portions of a plant show very different levels of lead retention. In coniferous forest,15 twigs retain more lead (approximately 28 mg kg–1) than tree bark (23 mg kg–1) which, in turn, retains more than the foliage (3 mg kg–1) and the highest concentration has been found in tree roots.16 Metals uptake by plants also depends on the nature of the soil and the height of the growth site.Lead concentrations in clouds and fog are usually higher than concentrations in rain and so, since high elevation areas usually have more precipitation and high rates of interception of cloud water, lead deposition may increase at high elevations. Lead in moss Virtually all particulate matter suspended in the air has a diameter of less than 20 µm.Metals suspended in this way can be deposited on the ground surface by rain out or wash out or simply settling under gravity. Alternatively, they may be intercepted by vegetation, by soil or by a water surface. Sphagnum moss obtains mineral nutrients from the air and can, therefore, be used to monitor airborne metal levels. A study of heavy metal retention in moss17 showed that lead and copper are retained more strongly than Ni, Co, Zn or Mn, a characteristic that means moss bags can be exploited as a natural field gauge to measure the deposition of lead to ground vegetation.We studied the relationship between lead deposition rate and distance from the roadside using bags of sphagnum moss placed at regular intervals over a 90 m length by the A27 in Hampshire.Figures 3(a), (b) and (c) show plots of mean lead deposition rate on moss [mean lead content (mg Pb y–1) divided by the exposure area (m2)] as a function of distance. The 1978 data [Figure 3(a)] show an overall decrease from 217 to 75 mg Pb m–2 y–1 with a local minimum at 23 m where the rate falls to 175 mg Pb m–2 y–1, and a local maximum of 209 mg Pb m–2 y–1 at 37 m.Figure 3. Lead deposition rate on moss samples as a function of distance from the side of the A27 roadway: (a) 1978 data; (b) 1984 data; (c) 1994 data. F E AT U R E C G G108 Green Chemistry August 1999C G F E AT U R E Green Chemistry August 1999 G109 1984 samples [Figure 3(b)] show a similar pattern ranging from 1025 mg Pb m–2 y–1 to 175 mg Pb m–2 y–1 with a local maximum of ca. 560 mg Pb m–2 y–1 and maximum of ca. 735 mg Pb m–2 y–1 at 20 and 35 m, respectively. In the 1994 analyses [Figure 3(c)] the deposition rate initially rises with distance reaching a broad maximum at a distance range of 30–50 m. The extremes of lead deposition rate are at distances of 50 m (a maximum) 300±70 mg Pb m–2 y–1 and 80 m (a minimum) ±25 mg Pb m–2 y–1.Beyond 50 m the deposition rate falls rapidly remaining approximately steady at 165±15 mg Pb m–2 y–1 by about 60 m. In other investigations18–20 the lead deposition rate in air decreased exponentially with distance, distinctly different from the rising and falling concentration we observed. We believe this is a consequence of the environment of the sampling site. A steep slope runs from the road surface down to the sampling posts so that vegetative growth on the slope and the boundary fence offer some screening.The second important factor is the upward dispersal of pollutants. Airborne lead concentration will be underestimated unless deposition rates take into account the small proportion of emitted lead that deposits in the immediate vicinity of the roadway. References 1 R.L. Boeckx, Anal. Chem., 58, 274A. 2 J. O. Nriagu, Sci. Total Environ, 1990, 92, 13. 3 D. Rosner and G. Markowitz, Amer. J. Public Health, 75, 344. 4 Department of the Environment Central Unit in Environmental Pollution, Lead in the environment and its significance to man: A report of an interdepartmental working group on heavy metals pollution Paper No. 2, HMSO, 1974. 5 V. M. Goldschmidt, Ind. Eng. Chem., 1935, 27, 110. 6 V. J. Kopinski and J. B. Upham, Arch. Environ. Health, 1967, 14, 589. 7 A. Archer and R. S. Barratt, Sci. Total Environ., 1976, 6, 275. 8 D. Turner, Chem. Br., 1980, 312. 9 P. L. Dartnell, Chem. Br., 1980, 308. 10 W. Keble-Martin, New Concise British Flora, Bloomsbury Books, London, 1982. 11 P. Little and R. D.Wiffen, Atmos. Environment, 1997, 11, 437. 12 G. H. Heichel and L. Hankin., J. Air Pollut. Control Ass., 1976, 26, 767. 13 F. Valerio, C. Brescianini, S. Lastraidi and S. Coccia, Int. J. Environ. Anal., Chem., 1993, 53, 1. 14 S. T. Y. Tong, Environ. Int., 1991, 17, 31. 15 A. J. Friedland and A. H. Johnson, J. Environ. Qual., 1985, 14, 322. 16 R. S. Turner, A. H. Johnson and D. Wang, Environ.Qual., 1985, 14, 305. 17 A. Ruhling and G. Tyler, Oikos, 1970, 21, 92. 18 R. O. McLean and B. Shields, Environ. Pollut., 1997, 14, 267. 19 N. I. Ward, R. D. Reeves and R. R. Brooks, Environ. Pollut., 1975, 9, 243. 20 A. C. Chamberlain, M. J. Heard, P. Little, D. Newton, A. C. Wells and R. D. Wiffen, Atomic Energy Research Establishment, AERE-R 9198, 1978. Conclusions Our results show, as expected, that vegetation lead levels decrease with distance from the roadside.At a distance greater than 20–30 m deposition falls approximately to background level. The 1978 and 1984 studies, made in the same area, showed as expected, that the lead content in the roadside grass increased with traffic density. The traffic volume has expanded considerably recently following upgrading of the road to an 8 lane highway but, over the same period, the use of unleaded fuel has increased and so a compensation effect was anticipated. Lead deposition is strongly dependent on the species of vegetation owing to differences in surface texture and to seasonality of growth and its interrelationship with the seasonal patterns in road traffic. Reduction in lead emissions will undoubtedly result in less environmental damage in future years but the continuing damage resulting from the lead that has already entered the environment is often underestimated, especially in terms of the lead entering the soil. The distribution of lead in the roadside soil has been studied and will be reported in another paper. Future monitoring of the site is also planned. ‘Reduction in lead emissions will reduce environmental damage—but lead already in the environment will cause continuing damage’

ISSN:1463-9262    

DOI:10.1039/a906801e

出版商:RSC    

年代:1999

数据来源: RSC

摘要:

Chemical Industry Swap Shop Chemical Industry Swap Shop with the theme Waste Minimisation and Monitoring took place in May 1999. The event was jointly organised by the Environmental Business Network, RIS—Yorkshire & Humber Chemical Sector, ETBPP (Environmental Technology Best Practice Programme) and the Green Chemistry Network. The day centred around a series of presentations covering legislation, industry examples of waste minimisation and developments in monitoring systems followed by a series of surgeries covering everything from Green Chemistry to Environmental Compliance to support available from ETBPP.Throughout the day there was the opportunity for delegates to visit various stands and to take a look at the latest monitoring equipment on the market. The day started with an overview, given by Peter Calow who is Director of the EBN (European Business Network) and Chair of the Government Advisory Panel on Hazardous Substances, of the implications for the chemical industry of legislation.Legislation can broadly be placed in two categories: l that concerned with Direct Toxicity Assessment i.e. it is the environmental consequences that are measured, not the nature or concentration of chemicals.l that concerned with answering the question: Are critical concentrations likely to be exceeded? As monitoring equipment becomes more sophisticated then there is an increasing trend to measure and therefore limit allowable concentrations to lower and lower levels—the only answer therefore is to prevent waste being produced in the first place.George Smith from Hickson & Welch gave an overview of what industry can achieve in terms of minimising energy, water, gas and nitrogen use as well as effluent production. Through taking a critical look at their activities and targeting process development Hickson’s have achieved savings of over £1.3 million pa at a cost of £300 000. The afternoon surgeries took the form of general discussion groups.The two Green Chemistry surgeries were well attended and attracted interest from large and small chemical companies, environmental specialists and research A Environmental monitoring using X-ray fluorescence analysis institutions. It was obvious that there is a lot of interest in what Green Chemistry can offer and we all enjoyed a lively debate.It is worth noting that the EBN are running a TIDE Programme until June 2001. This programme provides financial assistance for SME’s (Small to Medium Sized Enterprises) (from the Yorkshire & Humber region) to buy in specialist expertise for the development of environmentally friendly products and processes. Topics covered include clean technology, monitoring and clean-up technologies.Further information can be obtained from Fiona Raynor, EBN, 5 Palmerston Road, Sheffield, S10 2TE, UK. COST Chemistry Action: Symposium on ‘Towards Environmentally Benign Chemical Processes’ Chambery in France was the location for the recent COST Meeting which brought together sonochemists, collaborating through the COST Chemistry Action D10/0008/98, with green chemists.The objective of the meeting which was organised by Professor Jean Louis Luche, was to examine the possible contribution of sonochemistry to green chemistry. The lectures covered the strategic use of sonochemistry in synthetic organic What is COST? COST is the acronym for the French equivalent of ‘European Cooperation in the Field of Scientific and Technical Research’.It takes the form of ‘concerted actions’ coordinating nationally funded pre-competitive research. It is complementary to, and does not compete with, the EUREKA initiative and the EU’s Framework Programmes. There are 28 COST member countries: the 15 EU member states plus Iceland, Norway, Switzerland, the Czech Republic, Slovakia, Hungary, Poland, Turkey, Slovenia, Croatia, Malta, Estonia and Romania—plus the European Commission.E V E N T S C G G110 Green Chemistry August 1999Green Chemistry August 1999 G111 C G E V E N T S chemistry (Professor Ando), efficient oxidation processes assisted by ultrasound (Professor Sae Melo), sonochemical studies on cycloaddition reactions and related cyclisations (Professor Cintas), new processes for the use of agricultural resources as raw materials: the case for sucrose (Professor Queneau), ultrasound effects on photochemical and SET reactions (Professor Toma), sono-photodegradation of 2-chlorophenol (Professor Ragainin), sonolysis of organic compounds in water (Professor Petrier), sonolytic degradation of 1,2-dichloroethane and related compounds in natural ground water (Professor Peters) and scaling up sonochemistry: prospects and reality.Additionally Professors Clark and Sheldon gave talks on environmentally friendly organic synthesis and Professor Brunel described new mesoporous hybrid organic–inorganic materials as catalysts in fine chemistry. (http://www.cordis.lu/cost/home.html). Embassy commercial officers learn about green chemistry Over twenty commercial officers from UK embassies and high commissions throughout the world have recently spent two weeks in the UK on an industrybriefing course organised by ENTEC environmental consultants.The main responsibility of the commercial officers is to promote UK industry and expertise abroad; this course, aimed at demonstrating expertise within the UK environmental technology industry, included lectures, seminars and site visits —the highlight of which was a visit to the Millennium Dome.The Green Chemistry Network were invited to give a general talk on clean production, areas of UK expertise and technology. It was evident from the great enthusiasm and follow up questions that there is a real opportunity for both industry and consultants to exploit their know-how through collaboration, licensing etc.As expected the major areas of opportunity lie in the countries developing their chemical industry with places like China and India increasingly demanding that new chemical plants employ the latest clean, environmentally friendly technologies. The requirement for clean technology is truly universal: even highly developed countries such as Japan see a need for improved technology in the area of waste incineration, for example, where dioxin production is still a major concern. TMR - Programme Interuniversity Consortium "Chemistry for the Environment" European Commission - DG XII Announcing the second edition of the: SUMMER SCHOOL ON GREEN CHEMISTRY V e n e z i a , I t a l y September 6 - 12, 1999 A d m i t t e d a p p l i c a n t s w i l l r e c e i v e f u l l s c h o l a r s h i p s . Contacts: Prof. Pietro Tundo (Director): tundop@unive.it Dr. Alvise Perosa: alvise@unive.it Informations and application form: h t t p : / / w w w . u n i v e . i t / i n c a

ISSN:1463-9262    

DOI:10.1039/a906802c

出版商:RSC    

年代:1999

数据来源: RSC