Introduction to Green Chemistry

1. Introduction to Green Chemistry IN4GC Teaching Resources Prepared by Isla Milne

2. Outline • Why do chemicals matter? • The problem: Global chemical exposure and contamination • The (partial) solution: Green chemistry • 12 principles • Green chemistry in action: Case studies • Greener synthesis of ibuprofen • Dry cleaning without Perc • Boat paint without tin • Plastics from renewable sources (NatureWorks) • Role of business in green chemistry • Drivers for green chemistry: Business case for green chemistry • Ambec and Lanoie, 2008, Reinhardt, 1999 • EVA of 12 principles • Barriers to green chemistry • Conclusion

3. Why do chemicals matter? Chemicals and chemistry are everywhere Chemistry is life! C6H12O6 + 6O2 --> 6CO2 + 6H2O + energy

4. Why do chemicals matter? Chemicals and chemistry are everywhere Chemistry is life!

5. Why do chemicals matter? Chemicals and chemistry are everywhere • Chemicals are the “molecular building blocks” of our economy • Daily U.S. Chemical production and importation: 74 billion lbs • 82,000 chemical substances and millions of products in circulation

6. Why do chemicals matter? Global chemical production is growing rapidly • The chemical industry is valued at ~4 trillion USD (OECD, 2011)

7. Blue Jean Life Cycle Assessment: where/how are chemicals used? • Work in groups of 2 or three • Consider a pair of blue jeans. Brainstorm all of the places in the product life cycle where chemicals would be used • Pair up with another group and compare answers. • Report back to the class and discuss • What are the hazards associated with the chemicals identified in the lifecycle?

8. Chemicals: Double edged sword They are the solution to many of our problems.... But the cause of many hazards as well...

9. The problem: Global chemical contamination • Chemical pollution in the environment: The “environment” is not somewhere “out there”. We live in our environment • Synthetic chemicals contribute to a wide range of environmental and health hazards • Cancer • Neurodevelopmental problems • Obesity • Reproductive anomalies or dysfunction • Asthma and allergies • Neurodegenerative problems • Immune dysfunction • Climate change • Eutrophication • Biodiversity loss • Air pollution • Ozone depletion • Etc...huge data gaps!! ~700 new chemicals introduced into the market each year

10. Chemical contamination: Fromdisasters in the chemical industry... • In 1976, a chemical plant in Sevesco, Italy that manufactured pesticides and herbicides released a dense cloud of tetrachlorodibenzoparadioxin (TCDD), contaminating tens square miles of land. 2000 people were treated for dioxin poisoning. In 1984, a methylisocyanate leak at a Union Carbide chemical plant in Bhopal, India, killed thousands of people

11. ...and from gradual chemical pollution and exposure to everyday products • Examples: • Flame retardants • Cosmetics • Cleaning products • Paint • Plastics

12. Chemical contamination: Evidence from biomonitoring Chemicals found in pregnant women, umbilical cord blood, and breast milk: Mercury PCBs Flame retardants (e.g. PBDEs) Solvents Phenols (e.g. Bisphenol A) Stain repellants (e.g. Perfluorinatedsurfacants) Dioxins (e.g. TCDD) Perchlorate Plasticizers (e.g. Phthalates) Furans (e.g. TCDF) Polycyclic Aromatic Hydrocarbons (PAHs) Organochlorine pesticides (e.g. DDT, Hexachlorobenzene) Woodruff T. et al, 2011 Environ Health Persp.; Needham L. 2010 et al, EnvironmeSciTochnol Lakind, J.S. Et al, 2004 ToxicolApplPharma. Modified from the Berkeley Center for Green Chemistry slides.

13. Chemical contamination: Evidence from biomonitoring 287 synthetic chemical pollutants detected in umbilical cord blood Mercury Polyaromatic hydrocarbons (9) Polybrominateddibenzodioxins and furans (7) Perfluorinated chemicals (9) Polychlorinated dibenzodioxins and furans (11) Organochlorine pesticides (21) Polybrominateddiphenyl ethers (32) Polychlorinated napthalenes (50) Polychlorinated biphenyls (147) Modified from the Berkeley Center for Green Chemistry slides.

14. Problem: Global chemical contaminationSolution: Green chemistry! • Green chemistry (sometimes called “sustainable chemistry”) is a design strategy. It aims to prevent problems rather than clean them up later • Definition: “Design of chemical products and processes that reduce and eliminate the use and generation of hazardous substances” (Anastas and Warner, 1998) Risk = f(Hazard, Exposure) • Green chemistry is a RADICALapproach as the institutionalized and industrially embedded approach is to focus on exposure reduction. Green chemistry focuses on reducing the hazard. Video (2:31min): Martin Poliakoff on green chemistry: http://www.youtube.com/watch?v=_KYiLFkMQ_E

15. Key elements in a chemical process Products: Desired products and unwanted by-products Feedstock: starting material Medium and reagents: Where is the reaction happening? What needs to be added for the reaction to occur? Energy: Energy used to make reaction work, heating etc How can we make this process greener?? Adapted from presentation by Dr. Audrey Moores

16. Two different kinds of chemical plants...

17. 12 principles of green chemistry 1. PREVENTION: It’s better and easier to prevent waste than to deal with it after it’s formed. 2. ATOM ECONOMY: We should maximize the amount of material inputs that get incorporated into the final product. 3. LESS HAZARDOUS SYNTHESES: We should minimize hazardous by-products created by syntheses. 4. SAFER CHEMICALS: We should use design to preserve the efficacy of a function while reducing its toxicity. Anastas, P.T.; Warner, J.C. Green Chemistry: Theory and Practice, Oxfor University press, 1998

18. 12 principles of green chemistry 5. SAFER SOLVENTS AND AUXILIARIES: We should minimize the use of auxiliary substances wherever possible, or use ones that are non-toxic. 6. ENERGY EFFICIENCY: Energy requirements have environmental and economic impacts. We should conduct syntheses at ambient temperature and pressure to minimize energy costs. 7. RENEWABLE FEEDSTOCKS: Use renewable feedstocks 8. REDUCE DERIVATIVES: Unnecessary derivatization (using protecting or blocking groups during synthesis) should be avoided whenever possible to reduce waste. Minimise the number of steps in the reaction. Anastas, P.T.; Warner, J.C. Green Chemistry: Theory and Practice, Oxfor University press, 1998

19. 12 principles of green chemistry 9. CATALYSIS: Catalytic reagents are better than stoichiometric reagents in that they allow for lower temperatures and energy costs, and are reusable and therefore generate less waste. 10. DESIGN FOR DEGRADATION: Design products that are biodegradable at the end of their use. 11. REAL TIME POLLUTION PREVENTION: We should encourage methodologies to monitor the process of a reaction so as to detect the emergence of toxic by-products. 12. ACCIDENT PREVENTION: By minimizing the use of toxic substances and high energy processes, we also minimize the potential for Anastas, P.T.; Warner, J.C. Green Chemistry: Theory and Practice, Oxfor University press, 1998

20. Greening a chemical process • Products and byproducts • Minimize waste • Produce byproducts and products that are less toxic and biodegradable • Feedstocks • Use renewable feedstocks • Maximize the amount of inputs that make it into final product • Catalysts • play on activation energy and do more with less • Synthesis design • Minimize number of steps in reaction • Medium and reagents • Conduct reaction in water if possible • Use safer solvents • Energy • Use less • Energy • Conduct reactions at low temperature and pressure

21. 12 principles of green chemistry • GreenER. Not “green”. It’s all relative. There is no reaction in the world that would not have some impact - strive for continuous improvement. • Not all of the 12 principles will be addressed at the same time: there may be tradeoffs.

22. Green Chemistry in action: Ibuprofen • Developed by BHC (now part of BASF) in 1990s, the green route for Ibuprofen production produces more ibuprofen in less time and using less energy than the original process. This means cheaper products for the consumer with increased profits for the manufacturers. It saves 20,000 of waste/year! Poliakoff, M., 2007

23. Greening the ibuprofen process • Catalysts • play on activation energy and do more with less • Feedstocks • Maximize the amount of inputs that make it into final product (Atom economy = 77%) • Products and byproducts • Minimize waste (Less hydrofluoric acid used) • Synthesis design • Minimize number of steps in reaction (3 vs. 6) • Energy • Use less • Energy Medium and reagents

24. Green chemistry in action: Dry cleaning without Perc • Dry cleaning industry is heavily dependent on solvents (dry cleaning is not really dry!), 100,00 dry cleaners worldwide use percholorethylyne (perc) as primary solvent • Perc is toxic: everything perc comes in contact with must be handled as “hazardous waste” except the dry cleaned clothes • Supercritical carbon dioxide has been developed and demonstrated as a viable alternative • It is non-toxic, biodegredable, and avoids costly waste disposal and regulatory compliance • It has been shown to outperformperc in dry-cleaning applications Manley et al 2007.

25. Greening the dry cleaningprocess • Products and byproducts • Minimize waste • Produce byproducts and products that are less toxic and biodegradable Feedstocks Synthesis design Medium and reagents Energy

26. Green chemistry in action: Boat paint without tin • Tribytyltin (TBT) was widely used as an antifoulant on boats. It worked by gradually leaching from the hull killing the fouling organism in the surrounding area • It is extremely toxic to aquatic life, is an endocrine disrupting chemical, and very persistent in the environment • Regulations now restrict the use of TBT (e.g. banned in EU) • Rohm and Haas have developed an alternative based on thiazolone chemistry, which works by creating a hostile growing environment • New product is free of heavy metals, showed no chronic or reproductive toxicity to marine species, degrades readily when released into the environment Manley et al 2007.

27. Greening boat paint • Products and byproducts • Produce byproducts and products that are less toxic and biodegradable Feedstocks Synthesis design Medium and reagents Energy

28. Green Chemistry in Action: Plastics from renewable material • NatureWorksbiobased plastic resins: Joint venture between Cargill Inc and Dow Chemical • Received Presidential Green Chemistry Challenge Award in 2002 • Developed the first synthetic polymer class to be produced from renewable resources (corn), a potential substitute for petroleum-based polymers • Biodegradable (compostable) • Manufacturing sequence reduced consumption of fossil fuels by 30%-50% compared to conventional oil-based plastic resins Larson et al, 2006, Darden case study

29. http://www.natureworksllc.com/The-Ingeo-Journey/Eco-Profile-and-LCA/Eco-Profilehttp://www.natureworksllc.com/The-Ingeo-Journey/Eco-Profile-and-LCA/Eco-Profile

30. Greening the plastic production process • Catalysts • play on activation energy and do more with less (enzymatic fermentation process) • Products and byproducts • Produce byproducts and products that are less toxic and biodegradable • Feedstocks • Use renewable feedstocks (corn) Synthesis design Medium and reagents Many steps in the reaction are solvent free • Energy • Use less • energy

31. How businesses can contribute to the advancement (or not) ofGreen Chemistry • Fund and conduct R&D • Manufacture chemicals and products • Sell chemicals and products containing chemicals • Manage supply chains • Lobby for/against regulations • Distribute products containing chemicals • Run marketing campaigns • Conduct take-back initiatives (recovery and recycling) • Influence metrics used to measure performance (is environmental performance valued?) • Collaborate (e.g. with academia)

32. Drivers for green chemistry: It makes good business sense! • Reinhardt 1999 • Differentiating products • Managing your competitors • Saving costs • Managing environmental risks • Redefining markets • Ambec and Lanoie 2008 • Better access to certain markets • Differentiating products • Selling pollution control technologies • Risk management and relations with external stakeholders • Cost of Materials, Energy and Services • Cost of capital • Cost of Labor

33. Drivers for green chemistry: Business benefits of green chemistry innovation • Data set: Nominations for the Presidential Green Chemistry Awards, 2010 • Out of 60 green chemistry innovations coded, ~80% improved performance, ~85% reduced cost, ~45% reduced risk and ~35% increased regulatory compliance compared to the incumbent technology Milne and Maguire, 2011. ACS GCI Green Chemistry conference presentation

34. Drivers for green chemistry: Rising B2B demands “There are rising B2B demands for green chemicals,” says Rich Liroff, executive director of the Investor Environmental Health. Network. “Nike is now highlighting preferred green chemicals in its purchasing requirements. Staples also has developed a list of “bad actor chemicals;” and quite recently, several Group Purchasing Organizations in the health care sector, with buying power estimated at roughly $20 billion, developed a questionnaire for suppliers that focused on various sustainability questions, including the presence or absence of specific chemicals of concern.” - Rich Liroff, Environmental Health Investors Network Forbes Magazine, 2011, Better profits through green chemistry

35. Drivers for green chemistry: market for green chemicals is growing Source: Pike Research, 2011, Green chemistry research report

36. Which of the 12 principles are more likely to have high Economic Value Added? 1. PREVENTION: It’s better and easier to prevent waste than to deal with it after it’s formed. 2. ATOM ECONOMY: We should maximize the amount of material inputs used in the final product 3. LESS HAZARDOUS SYNTHESES: We should minimize hazardous by-products created by syntheses. 4. SAFER CHEMICALS: We should use design to preserve the efficacy of a function while reducing its toxicity. 5. SAFER SOLVENTS AND AUXILIARIES: We should minimize the use of auxiliary substances wherever possible, or use ones that are non-toxic. 6. ENERGY EFFICIENCY: Energy requirements have environmental and economic impacts. We should conduct syntheses at ambient temperature and pressure to minimize energy costs. 7. RENEWABLE FEEDSTOCKS: Use renewable feedstocks 8. REDUCE DERIVATIVES: Unnecessary derivatization (using protecting or blocking groups during synthesis) should be avoided whenever possible to reduce waste. 9. CATALYSIS: Catalytic reagents are better than stoichiometric reagents in that they allow for lower temperatures and energy costs, and are reusable and therefore generate less waste. 10. DESIGN FOR DEGRADATION: Design products that are biodegradable at the end of their use. 11. REAL TIME POLLUTION PREVENTION: We should encourage methodologies to monitor the process of a reaction so as to detect the emergence of toxic by-products. 12. ACCIDENT PREVENTION: By minimizing the use of toxic substances and high energy processes, we also minimize the potential fo

40. Barriers to green chemistry • Upfront costs (R&D, infrastructure etc) • Uncertainty and risk (regulatory and scientific) • CBI – hard to get suppliers to tell you what is in their products • Data, safety and technology gaps (Wilson and Schwarzman, 2008) Regulatory barriers • Regulations are very fragmentation (REACH, TSCA, Chemicals Management Plan etc) • How safe is safe? Two models: (a) Company must produce evidence of safety (e.g. FDA (drugs))  default assumption is that the chemicals are hazardous (b) Government must produce evidence of harm (Toxic Substances Control Act, most other laws)  default assumption is that chemicals are safe • REACH (EU legislation) is starting to set a good example, moves towards model (a)

41. Barriers to green chemistry: Data gaps “Not enough information is available on how many of the approximately 30,000 substances currently estimated to be covered by the REACH proposals have dangerous properties. [...] However, of the new substances assessed under existing EU legislation, around 70% have been shown to have one or more dangerous properties. An unknown but potentially significant proportion of all chemical substances will enter the environment and reach sufficiently high concentrations to induce adverse effects” European Commission, 2003, REACH Extended Impact Assessment, p27

42. Barriers to green chemistry: Data gaps “All substances are poisons: there is no substance which is not a poison. The right dose differentiates a poison from a remedy” Paracelsus, 1493-1591 “The dose of the mixture makes the poison, but differently for different individuals and differently at different times during growth and development” Peter Motague, 2002 • Our understanding of what differentiates a “poison from a remedy” is evolving, but there is still a lot we don’t know • Traditional methods of testing for toxicology are not effective for many toxicology endpoints: e.g. Endocrine disruption

43. Conclusion • To be successful, green chemistry requires an interdisciplinary strategy in education, research and service • You don’t have to be a chemist or a toxicologist, you just have to know what you don’t know so you can ask one! • Green chemistry makes good business sense • Chemical exposures and global chemical contamination: • No single problem • No single solution • Green Chemistry has the potential to be part of the solution