2. 12 Principles of Green Chemistry Principle # 1 It Is Better to Prevent Waste than … Why ?

3. 12 Principles Principle 1 – Prevention 1200 million tons of waste is produced in the US annually (only 20 %) 250 million tons is Municipal Solid Waste (MSW) 400 million tons hazardous waste generated worldwide annually The cost of waste is staggering. Estimate is in 1992 the US spent $ 115 billion on waste treatment and disposal. 94 % of resources that go into a product is discarded as waste

4. What is in Municipal Solid Waste ? EPA Dec., 2011 Most is paper and cardboard ! plastics

5. we’re doing better

6. What Gets Recycled the Most ?

8. Solid Waste Management What are the options ? incineration, biodegradation, reuse recycling, source reduction

9. US Waste Profile is Flat What to do with Waste

10. Toxic Release Inventory (TRI) 2011

11. The Fate of Waste In 2012 0.28 billion tons of plastic was produced globally By 2050 estimate is for 33 billion tons (100 fold increase)

12. What’s with Waste ? Incineration heat in plastics > coal Recycling 1995 1 container in 3 2010 1 container in 7 Recycled content products products made from material that would have been discarded Postconsumer content used material that would have been discarded Preconsumer content waste left over from manufacture Recyclable products What examples can we identify ?

13. The Cost of Waste J.H. Clark, Green Chemistry, Feb., 1999, p. 1-9

14. We each generate 4.5 lbs/person/day We recycle 1.5 lb/person/day We dispose of 3 lbs/person/day http://www.epa.gov/wastes/nonhaz/municipal/pubs/msw_2010_rev_factsheet.pdf 54.2% 34.1 % 11.7% 2010 250 “only” 12 % Most !

15. Who Generates ? Where Does it Go ? WASTE IMPORTERS TONS 1. Pennsylvania 9,764,000 2. Virginia 3,891,000 3. Michigan 3,124,000 4. Illinois 1,548,000 5. Indiana 1,531,000 WASTE EXPORTERS TONS 1. New York 5,600,000 2. New Jersey 1,800,000 3. Missouri 1,793,000 4. Maryland 1,547,000 5. Massachusetts 1,218,000

16. Who Generates ? Where Does it Go ? WASTE IMPORTERS TONS 1. Pennsylvania 9,764,000 2. Virginia 3,891,000 3. Michigan 3,124,000 4. Illinois 1,548,000 5. Indiana 1,531,000 WASTE EXPORTERS TONS 1. New York 5,600,000 2. New Jersey 1,800,000 3. Missouri 1,793,000 4. Maryland 1,547,000 5. Massachusetts 1,218,000

17. ATOM ECONOMY 1998 Barry Trost, Stanford University “ Because an Atom is a Terrible Thing to Waste” Q: How many of the atoms of the reactant(s) are incorporated into the desired final product and how many are wasted? A: It depends on the type of reaction involved.

18. 2 Principles of Green Chemistry Principle # 2 Do It Atom Economically B.M. Trost, Angew. Chem., Int.Ed, 1995, 34, 259-281; Science, 1991, 254, 1471-1477. Synthetic methods should be designed so as to maximize the incorporation of all materials (starting materials, feedstocks, reactants, reagents) used in the process into the desired final product. Yield = amount obtained/amount theoretically expected % Yield = (amount obtained/amount predicted) x 100 % Atom Economy = mass of atoms in product/mass of all atoms used AE = molecular weight of product / sum of all molecular weights in starting reactants and reagents

19. “E-Factor” How do you make a green M&M ? orange + red + brown = green orange + red + brown = green + orandbrow Atom Economy = 5/(6+3+5) =5/14 = 36% E FACTOR = waste/product = 9/5 = 1.8

20. “And the best E FACTOR goes to …

22. “E” Factor R.A. Sheldon Chemistry & Industry (London) 1992, 903-906 Green Chemistry, 2007, 9(12), 1261-1384 E factor = mass waste / mass product = (mass in – mass all outputs) / total mass product Total Waste (ton) 10 6 10 5 10 4 10 3

24. Plastics and Polymers-What Kinds?

25. Plastics and Polymers Natural Synthetic

26. Plastics and Polymers Natural Synthetic Silk Polyethylene, PE, HDPE, LDPE Cotton Polytetrafluoroethylene-Teflon Cellulose Nylon Starch Polyester Wood Kevlar Protein Lexan Lignan PETE Hair PP, PS, PVC

28. Plastics and Polymers How are they made? How are they used? How are they disposed of? How are they recycled?

29. Plastics and Polymers How Made ? 1) Addition C=C + C=C => [-C-C-C-C-] N 2) Condensation -A-A-[OH + H]-B-B- => -A-A-B-B- (- H 2 O) 3) Co-polymerization with 2 different monomers A-B-A-B- How Processed ? molded, cast, extruded, drawn, laminated What Types ? Thermoplastic (90%) - melted & reshaped PETE, PVC, PE, PP, PS usually linear chains Thermoset (10%) - irreversibly heat cured & inflexible urea resins, epoxys, melamine usually crosslinked

30. Condensation Polymer (- water) PETE precursor

31. Plastics and Polymers Polyethylene HDPE LDPE Polypropylene PP Polystyrene PS Polyvinyl chloride PVC Polyethylene terephthalate PETE

32. Plastics Greek πλαστικός (plastikos) meaning capable of being shaped or molded πλαστός (plastos) meaning molded 123 4567123 4567

33. 1 PET (PETE) polyethylene terephthalate, is commonly found in 2-liter soft drink bottles,polyethylene terephthalate water bottles, cooking oil bottles, peanut butter jars. 2 HDPE high-density polyethylene, (linear chains) is commonly found inhigh-density polyethylene detergent bottles, milk jugs, bags, lids, toys (1950 1 st use-hula hoops !) 3 PVC polyvinyl chloride, is commonly found in plastic pipes, outdoor furniture,polyvinyl chloride siding, floor tiles, shower curtains, rain wear, clamshell packaging. 4 LDPE low-density polyethylene, (branched chains) is commonly found in dry-cleaninglow-density polyethylene bags, produce & trash bags, trash can liners, and food storage containers. 5 PP polypropylene, is commonly found in bottle caps, drinking straws, food containers.polypropylene 6 PS polystyrene, is commonly found in "packing peanuts", cups, plastic tableware,polystyrene meat trays, take-away food clamshell containers. 7 Other others including polycarbonate is commonly found in food containersothers including polycarbonate 1885 First plastic made by Alexander Parkes – “Parkesine” made from cellulose ! Today 560 billion lbs plastics produced every year ~ 260 billion lbs (46 %) produce waste; long degradation time

34. 1Polyethylene Terephthalate (PET, PETE) - Clarity, strength, toughness, barrier to gas and moisture, resistance to heat. 2High Density Polyethylene (HDPE) - Stiffness, strength, toughness, resistance to chemicals and moisture, permeability to gas, ease of processing, and ease of forming. 3 Vinyl (Polyvinyl Chloride or PVC) - Versatility, clarity, ease of blending, strength, toughness, resistance to grease, oil and chemicals. 4 Low Density Polyethylene (LDPE) - Ease of processing, strength, toughness, flexibility, ease of sealing, barrier to moisture. 5 Polypropylene (PP) - Strength, toughness, resistance to heat, chemicals, grease and oil, versatile, barrier to moisture. 6 Polystyrene (PS) - Versatility, insulation, clarity, easily formed 7 Other - Use of this resin identification code indicates that the plastic product is made with a resin other than the six listed above, or is made of more than one resin listed above, and used in a multi-layer combination. Properties are dependent on resin or combination of resins All of the plastic products carrying one of the above listed plastic identification codes can be used for making recycled plastic products. http://www.plasticrubbermachines.com/articles/plastic-id-codes.html

35. Poly (Many) Ethylene Linear-rigid, opaque, high density, high melting point Branched-flexible, translucent, lower density, lower melting point

36. Plastics and Polymers from Petroleum Polyethylene (PE)

37. Greener PE BioPE ! From Braskem (Brazil) 2010 sugar cane, beets, -> ethanol -> ethene -> PE Per ton PE produced (200,000 ton capacity) 2.5 tons CO 2 captured in this process vs. 3.5 tons CO 2 emitted in traditional process

38. PP, PS, PVC “head-to-tail”

40. PETE P oly e thylene Te rephthlate Nathaniel Wyeth 4 billion lbs/year ! Only 25% mechanically recycled Most important commercial polyester Half of all polyester carpet in US made from recycled PET bottles Two issues – raw material resource and disposal http://www.nytimes.com/2012/01/13/health/research/surgeons-transplant-synthetic- trachea-in-baltimore-man.html?_r=1&scp=1&sq=plastic%20trachea&st=cse

41. Problems with PETE bottles 1) Made from a non-renewable resource (1939) 2) Does not biodegrade 3) Cannot be recycled on a closed-loop system In the process of making the bottle, two different dimers are zipped together to form the co-polymer DMT Ethylene Glycol HO-CH 2 -CH 2 -OH

42. This zipping (condensation reaction) produces the co-polymer PETE

43. Lifecycle of a PET beverage bottle What’s wrong with this picture ? Crude oil  Xylene  DMT  PET

44. Recycling can make these... But we still use PET bottles so we are still using petroleum

45. What if the Lifecycle of a PET beverage bottle looked like this…

46. Presidential Green Chemistry Award Nominee 1997 DuPont Company for Petretec the unzipping of the polymers in PET Real World Cases in Green Chemistry I p.25

47. The Petretec depolymerization process chemical reaction http://academic.scranton.edu/faculty/CANNM1/industrialchemistry/industrialchemistrymodule.html includes scrap PET The DuPont Company at their Cape Fear plant in North Carolina uses this process to recover 100 million lbs of PETE annually. Saves 0.5 lb xylene (oil) per lb DMT recovered. DMT Ethylene Glycol

48. The Dupont Petretec Process For Polyester Regeneration

49. Petretec Polyester Regeneration Methanolysis Reactor 260-300 o C 340-650 kPa

50. Has the problem been solved? Made from a non-renewable resource The non-renewable resource is now renewable Does not biodegrade This would be solved if we could get everyone to a Petretec processing plant Cannot be recycled on a closed-loop system Petretec is a closed-loop recycling system

51. Which States Have Bottle Bills ?

53. BioDegradable Polymers Poly vinyl alcohol Poly glycolic acid Poly ethylene oxide) Poly caprolactone

54. Bioplastics & Bio-based Plastics starch, cellulose, polyester, polylactic acid (PLA) polyhydroxybutyrate (PHB)

55. Bio Plastics Cargill NatureWorks PLA biopolymer Sorona DuPont platform chemical “BioPDO” http://www2.dupont.com/Renewably_Sourced_Materials/en_US/ DuPont™ Sorona® contains 37% renewably sourced material (by weight) derived from corn. A breakthrough in polymer science, the key ingredient in Sorona® is DuPont Tate & Lyle Susterra™ renewably sourced™ propanediol, which replaces petroleum-based 1,3-propanediol. Sorona® is an advanced material that offers a unique combination of attributes that are beneficial in a wide variety of applications. Whether it is textile fibers and fabrics for home interiors and apparel, carpeting, or a variety of packaging applications such as films, sealants, foams, and rigid containers, Sorona® imparts distinctive, value-added characteristics. Sorona® is commercially available. Earth Shell eco-dinnerware http://www.earthshell.com/

56. Earth Shell http://www.earthshell.com/ http://www.earthshell.com