Green Chemistry

Sponsored by:

“ Chemistry has an important role to play in achieving a sustainable

civilization on earth.”

— Dr. Terry Collins, Professor of ChemistryCarnegie Mellon University

Green chemistry is the design of products and processes reducing or eliminating hazardous

substances.

Green Chemistry is a subset of Design for Environment applying innovative scientific

solutions to product manufacturing.

Definition

Definition: An Industry Example

Shaw’s Green Chemistry Goals

Develop a sustainable thermopolymer platform for the future.

Cradle to cradle sustainability of face fiber and backing—100% of the product.

No increase in price. No sacrifice of performance. No loss of design variety.

GREEN CHEMISTRY SUPPORTS SUSTAINABILITY BY:

• Making chemicals safe for our health & environment,

• Using industrial processes that reduce or eliminate hazardous chemicals, &

• Designing more efficient processes that minimize waste

GREEN CHEMISTRY MEANS…

• Preventing pollution before it happens rather than cleaning up the mess later.

• Saving companies money by using less energy and fewer/safer chemicals, thus reducing costs & impacts of pollution.

• Mitigating climate change, water & resource depletion, & growing demands for safer food and cleaner energy

1. Prevention: it is best to prevent pollution/waste

2. Atom Economy: synthetic methods should maximize the incorporation of all materials used in the process into the final product

3. Less Hazardous Chemical Syntheses: synthetic methods should use and generate non toxic substances

Green Chemistry Principles

4. Designing Safer Chemicals: products should be nontoxic & designed to effect their desired function

5. Safer Solvents and Auxiliaries: auxiliary substances (e.g., solvents, separation agents) should be avoided and innocuous when used

6. Design for Energy Efficiency: Run chemical reactions at ambient temperature and pressure

Green Chemistry Principles 4,5,6

7. Use of Renewable Feedstocks: raw material or feedstock should be renewable rather than depleting

8. Reduce Derivatives: Avoid unnecessary derivatization (use of blocking groups, protection/deprotection, temporary modification of physical/chemical processes) because such steps require additional reagents and can generate waste

Green Chemistry Principles 7,8

9. Catalysis: Catalytic reagents (as selective as possible) are superior to stoichiometric reagents which are used in excess and work only once

10. Design for Degradation: Chemical products should be designed so that at the end of their function they break down into innocuous degradation products

Green Chemistry Principles 9,10

11. Analyze in real time to prevent pollution: Include in-process real-time monitoring and control during syntheses to minimize or eliminate byproducts

12. Minimize accidents: Design chemicals and their forms (solid, liquid, gas) to minimize the potential for chemical accidents, releases, explosions, and fires

Green Chemistry Principles 11,12

Presidential Green

Chemistry Award

Sustainable thermo-plastic platform for the future.

Closed-loop recovery of face yarn and all backing components.

No increase in price and no loss of performance or variety.

http://www.epa.gov/greenchemistry/dsca03.html

Recognizing Product Excellence:Presidential Green Chemistry Award Recipient

Shaw EcoWorxShaw EcoWorx™™ Carpet Tile Carpet Tile

Shaw Industries is the world’s largest manufacturer of carpets for home and business – and leader in sustainability.

NO

NO

R

R

ON

O

NFe

Y n–

III

X

X

TetraAmidoMacrocyclic Ligand TetraAmidoMacrocyclic Ligand or TAML® Activatorsor TAML® Activators

1.Design

molecular “cup” thought to be suitable for

attaining long-lived catalysts

1.Design

molecular “cup” thought to be suitable for

attaining long-lived catalysts

3. Characterize broken cup and identify

breaking point

3. Characterize broken cup and identify

breaking point

2. Oxidize catalyst until cup “breaks”

2. Oxidize catalyst until cup “breaks”

4. Modify weak siteto be more robust

4. Modify weak siteto be more robust

Designing Ligands for Oxidizing Complexes, T. J. Collins Accounts Chem. Res., 1994, 27, 279-285.TAML® Oxidant Activators: A New Approach to the Activation of H2O2 for Environmentally

Significant Problems, T. J. Collins Accounts Chem. Res., 2002, 35, 782-790

The Design Protocol

That Led to TAML® Catalysts

• formed from biochemically common elements– prototype exhibits v. low toxicity

• beginning of “dial-a-lifetime” catalysis• economical to synthesize• water-soluble• usable from pH 1 to 13• efficient users of peroxide

—fast peroxidase/slow catalase• 10 US patents, >70 counting foreign nationalizations • effective at 0.1 to 4 ppm = nM to low M• amenable to modifications for capturing novel selectivity• currently being produced for small scale commercial uses

• formed from biochemically common elements– prototype exhibits v. low toxicity

• beginning of “dial-a-lifetime” catalysis• economical to synthesize• water-soluble• usable from pH 1 to 13• efficient users of peroxide

—fast peroxidase/slow catalase• 10 US patents, >70 counting foreign nationalizations • effective at 0.1 to 4 ppm = nM to low M• amenable to modifications for capturing novel selectivity• currently being produced for small scale commercial uses

TAML® Catalyst Features

TAML® Activators Are Broadly Useful Oxidation Catalysts

TAML® Activators Are Broadly Useful Oxidation Catalysts

TEXTILESdye bleaching,

effluent decolorization

PULP AND PAPER pulp bleaching,

effluent AOX and color removal

WATER CLEANINGhalogenated aromatics and

organics destruction

LAUNDRYDye transfer inhibition,

stain removal

CHEM/BIO DEFENSERapid destruction of chem-bio

warfare/terrorism agents

plusPETROLEUM REFINING

rapid oxidation of sulfurcontaminants, other uses

Shaw EcoWorx Carpet

PVC & polyurethane substitute for carpet backing

Made from nontoxic polyolefin

Recyclable & contains fewer harmful chemicals

http://www.epa.gov/greenchemistry/dsca03.html

Recognizing Product Excellence:Presidential Green Chemistry Award Recipient

Production (SY)

0

1000000

2000000

3000000

4000000

1998 1999 2000 2001 2002

Production (SY)

Production ($)

0 20,000,000 40,000,000 60,000,000 80,000,000

1999 2000 2001 2002 2003

Production ($)

EcoWorx™ Production

EcoWorx represented 70% of all carpet tile production at Shaw by the end of 2003

In June 2004 Shaw announced it would exit PVC use by year-end In June 2004 Shaw announced it would exit PVC use by year-end in favor of the EcoWorx sustainable metallacene catalyzed in favor of the EcoWorx sustainable metallacene catalyzed polyolefin compound.polyolefin compound.

EcoWorxEcoWorx™™ Carpet TileCarpet Tile

Grinding and airflow

separate backing from

fiber for sustainable recycling

•LDPELDPE - flexible base - flexible base polymerpolymer

•HDPE/MAHHDPE/MAH - - adhesion and filler adhesion and filler compatibilitycompatibility

•Alaphatic tackifierAlaphatic tackifier - - adhesion and flow adhesion and flow modificationmodification

•Coal Fly AshCoal Fly Ash – – inorganic fillerinorganic filler

•OilOil – adhesive – adhesive compatibilizercompatibilizer

•Nylon 6Nylon 6 – caprolac- – caprolac-tam monomertam monomer

•25% postindustrial 25% postindustrial recycled contentrecycled content

•Over Over 20 million lbs 20 million lbs of recovered nylonof recovered nylon used in 2003used in 2003

•N6 depolymerizationN6 depolymerization by Honey-wellby Honey-well

•recovered recovered caprolactam caprolactam repolymerizedrepolymerized

Backing Chemistry Fiber Chemistry

IN SUMMARY,GREEN CHEMISTRY IS…

• Scientifically sound

• Cost effective &

• Leads toward a sustainable civilization

For further information on real world green chemistry

http://www.chemistry.org/portal/a/c/s/1/acsdisplay.html?DOC=education\greenchem\cases.html

For introductory readings in green chemistry http://www/chemistry.org/portal/a/c/s/1/

acsdisplay.html?DOC=education\greenchem\greenreader.html

Thanks to the Sponsors: