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
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
plastics
Most is paper and cardboard !

5. we’re
doing better

6. What Gets Recycled the Most ?

7. 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 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 container in 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
Ca. 94% of the resources that go into making a proditc is discarded as waste

14. We each generate 4. 5 lbs/person/day We recycle 1
We each generate 4.5 lbs/person/day We recycle 1.5 lb/person/day We dispose of 3 lbs/person/day
2010
11.7%
“only”
12 %
54.2%
34.1 %
Most !
250

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

16. Who Generates ? Where Does it Go ?
WASTE IMPORTERS TONS 1. Pennsylvania 9,764, Virginia 3,891, Michigan 3,124, Illinois 1,548, Indiana 1,531,000 WASTE EXPORTERS TONS 1. New York 5,600, New Jersey 1,800, Missouri 1,793, Maryland 1,547, 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. Yield = amount obtained/amount theoretically expected
2 Principles of Green Chemistry Principle # Do It Atom Economically B.M. Trost, Angew. Chem., Int.Ed, 1995, 34, ; Science, 1991, 254, 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 EFACTOR goes to …

21. “And the best EFACTOR goes to …

22. “E” Factor R.A. Sheldon Chemistry & Industry (London) 1992, Green Chemistry, 2007, 9(12), E factor = mass waste / mass product = (mass in – mass all outputs) / total mass product
Total Waste (ton)
106
105
104
103

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
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 ? How Processed ? What Types ?
1) Addition C=C + C=C => [-C-C-C-C-]N
2) Condensation -A-A-[OH + H]-B-B- => -A-A-B-B- (- H2O)
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

32. How Was Spring Break ?
Did you practice being green ? How so ? Our class – modify teams assignments schedule and syllabus read “Plastics-AToxic Love Story” Case Study Presentation and Poster Plastics Journal Term Paper No Final Exam

33. Plastics Journal Assignment
What do you use that is plastic ? What kinds of plastic? How much plastic do you use? How much do you dispose of? What do you use that is not plastic? What materials are these? How much non plastic do you use?

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

35. Plastics Greek πλαστικός (plastikos) meaning capable of being shaped or molded πλαστός (plastos) meaning molded

36. Plastics Greek πλαστικός (plastikos) meaning capable of being shaped or molded πλαστός (plastos) meaning molded
1 PET (PETE) polyethylene terephthalate, is commonly found in 2-liter soft drink bottles,
water bottles, cooking oil bottles, peanut butter jars.
2 HDPE high-density polyethylene, (linear chains) is commonly found in
detergent bottles, milk jugs, bags, lids, toys ( st use-hula hoops !)
3 PVC polyvinyl chloride, is commonly found in plastic pipes, outdoor furniture,
siding, floor tiles, shower curtains, rain wear, clamshell packaging.
4 LDPE low-density polyethylene, (branched chains) is commonly found in dry-cleaning
bags, produce & trash bags, trash can liners, and food storage containers.
5 PP polypropylene, is commonly found in bottle caps, drinking straws, food containers.
6 PS polystyrene, is commonly found in "packing peanuts", cups, plastic tableware,
meat trays, take-away food clamshell containers.
7 Other others including polycarbonate is commonly found in food containers
First plastic made by Alexander Parkes – “Parkesine” made from cellulose !
Today ca. 600 billion lbs plastics produced every year (300 lbs/person/year)
ca. 7 % is recycled; long degradation time

37. Polyethylene Terephthalate (PET, PETE) - Clarity, strength, toughness, barrier to gas and moisture, resistance to heat.
High 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.

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

39. Plastics and Polymers from Petroleum Polyethylene (PE)

40. Greener PE BioPE !
From Braskem (Brazil) 2010 sugar cane, beets, -> ethanol -> ethene -> PE Per ton PE produced (200,000 ton capacity) 2.5 tons CO2 captured in this process vs. 3.5 tons CO2 emitted in traditional process

41. PP, PS, PVC “head-to-tail”

43. PETE PolyethyleneTerephthlate Nathaniel Wyeth 90 billion lbs/year
PETE PolyethyleneTerephthlate Nathaniel Wyeth 90 billion lbs/year ! Only 31% mechanically recycled in US; 50% in Europe Most important commercial polyester Half of all polyester carpet in US made from recycled PET bottles Two issues – raw material resource and disposal

44. 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-CH2-CH2-OH

45. This zipping (condensation reaction) produces the co-polymer PETE
To make this revolutionary molecule

46. The Latest ! Kohei Oda (Kyoto Institute of Technology) and Kenji Miyamoto (Keio University) screened 250 sediment, soil, wastewater, and activated sludge samples from a PET bottle recycling facility in Sakai, Japan. Chem&EngNews 3/24/16; Science  11 Mar 2016: Vol. 351, Issue 6278, pp DOI: /science.aad6359
45 million metric tons/year

47. Fig. 1 Microbial growth on PET.
Microbial growth on PET. The degradation of PET film (60 mg, 20 × 15 × 0.2 mm) by microbial consortium no. 46 at 30°C is shown in (A) to (C). The MLE (modified lettuce and egg) medium (10 mL) was changed biweekly. (A) Growth of no. 46 on PET film after 20 days. (B) SEM image of degraded PET film after 70 days. The inset shows intact PET film. Scale bar, 0.5 mm. (C) Time course of PET film degradation by no. 46. PET film degradation by I. sakaiensis 201-F6 at 30°C is shown in (D) to (H). The YSV (yeast extract–sodium carbonate–vitamins) medium was changed weekly. (D to F) SEM images of I. sakaiensis cells grown on PET film for 60 hours. Scale bars, 1 μm. Arrow heads in the left panel of (D) indicate contact points of cell appendages and the PET film surface. Magnifications are shown in the right panel. Arrows in (F) indicate appendages between the cell and the PET film surface. (G) SEM image of a degraded PET film surface after washing out adherent cells. The inset shows intact PET film. Scale bar, 1 μm. (H) Time course of PET film degradation by I. sakaiensis.
Shosuke Yoshida et al. Science 2016;351:
Published by AAAS

48. Lifecycle of a PET beverage bottle What’s wrong with this picture ?
Crude oil 
Xylene 
DMT  PET
So what is the lifecycle of that bottle – The petroleum is mined, refined and made into a polymer and a bottle. Then it is used and discarded…then what?
It either goes into a landfill where it will be for about a 100,000 years or…

49. Recycling can make these ...
Chemists have already figured out a way to make PET bottles, Lumber substitutes (like those green plastic park benches) ,Flower pots, Pipe , Toys, pails and drums Traffic barrier cones,Trash cans into carpets, insulation in clothing and guard rails for roads. So chemists have successfully figured out how to recycle PET in an open-loop system but how do we make it closed loop
But we still use PET bottles so we are still using petroleum

50. What if the Lifecycle of a PET beverage bottle looked like this…
The bottle that has already been made from petroleum is used, discarded and then through the brilliance of green chemistry, is made back into the very same bottle

51. 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
The petretec process is the unzipping of the polymer back to two dimers which are perfectly in tact so that they can once again be made back onto PETE.

52. The Petretec depolymerization process chemical reaction
DMT Ethylene Glycol
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.
The scrap PET is dissolved in DMT at a temperature of above 220 degrees celcius and then reacted with methanol. The PET is then Transesterified which means that one ester group type was converted to another ester group type to produce DMT and ethylene glycol again which can be made to make a new PET bottle

53. The Dupont
Petretec
Process
For
Polyester
Regeneration

54. Petretec Polyester Regeneration
Methanolysis Reactor
oC kPa

55. 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
Green chemistry provides a framework for scientists to be able to solve problems for society

56. PET from Biomass !

59. Which States Have Bottle Bills ?

60. Which States Have Bottle Bills ?

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

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

63. Bio Plastics Cargill NatureWorks PLA biopolymer
Sorona DuPont platform chemical “BioPDO”
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

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