ecomate® Environmentally Benign Foam Blowing Agent 12th Annual Green Chemistry & Engineering Conference 26June08

Need for Insulation Saves Energy & Resources Protects Environment Reduces Heat Losses: Convective, Conductive, Radiant Heat Minimize Drafts Protects Environment Efficiency depends on Resident Gases Dry Air – Fiberglass, Cellulose Blowing Agents - Foams

Polyurethane Chemistry Polyol + Isocyanate → Urethane R-OH + R’-N=C=O → R’-N-C=O | \ H OR Both multi - functional

PU Chemistry, cont Other additives Surfactant - silicone Catalysts - tertiary amines & metal salts Misc additives – Fire Retardants, property enhancers Blowing Agent(s)

Physical Blowing Agents Requirements for PU foams Boiling Point below → just above RT Non-Reactive with ingredients used Solubilizes all Raw Materials Non-Soluble to final Polymer Foam Affords good Thermal Properties Environmentally Benign Non Flammable

BA History Water CFCs HCFCs HFCs Reacts with ISO → CO2 + Polyurea 11 Trichloro-fluoro methane BP 23.7 C 12 Dichloro-difluoro methane BP -29.8 C ↓ HCFCs 141b Dichloro-fluoro ethane BP 32.2 C 22 Chloro-difluoro methane BP -40.8 C HFCs 245fa 1,1,1,3,3 Pentafluoro propane BP 15.3 C 365mfc Pentafluoro butane BP 40.2 C 134a Tetrafluoro ethane BP -26.2 C

Blowing Agents - Environmental Characteristics   ODP GWP100 VOC ODP – Ozone Depletion Potential GWP – Global Warming Potential VOC – Volatile Organic Compound Zero ODP & GWP

Blowing Agents - Environmental Characteristics   ODP GWP100 VOC CFC 11 1 4750 NO CFC 12 10,900 ODP – Ozone Depletion Potential GWP – Global Warming Potential VOC – Volatile Organic Compound Zero ODP & GWP

Blowing Agents - Environmental Characteristics   ODP GWP100 VOC CFC 11 1 4750 NO CFC 12 10,900 HCFC 141b 0.1 725 HCFC 22 0.05 1810 Zero ODP & GWP

Blowing Agents - Environmental Characteristics   ODP GWP100 VOC CFC 11 1 4750 NO CFC 12 10,900 HCFC 141b 0.1 725 HCFC 22 0.05 1810 HFC 134a 1430 HFC 245fa 1030 Zero ODP & GWP

Blowing Agents - Environmental Characteristics   ODP GWP100 VOC CFC 11 1 4750 NO CFC 12 10,900 HCFC 141b 0.1 725 HCFC 22 0.05 1810 HFC 134a 1430 HFC 245fa 1030 Cyclopentane 11 YES Zero ODP & GWP

Blowing Agents - Environmental Characteristics   ODP GWP100 VOC CFC 11 1 4750 NO CFC 12 10,900 HCFC 141b 0.1 725 HCFC 22 0.05 1810 HFC 134a 1430 HFC 245fa 1030 Cyclopentane 11 YES Me Formate negligible MF - an attractive long term environmental option Zero ODP & GWP

Ecomate® [Methyl Formate] Properties CH3OOCH 31.5 ºC -32 ºC 5 - 23% 10.7 * 586 >450 ºC 0.982 60 * calculated Clear, Colorless, Flammable Liquid Boiling Pt Flash Point LEL \ UEL LAMBDA, gas @ 25 °C VP (mm Hg @ 77 °F) Auto Ignition Temp Specific Gravity Molecular Weight Ecomate is ONLY product on market that is Zero ODP, GWP, and VOC !

GAS LAMBDA VALUES

Optimal Foam k-Factors CFC-11 0.11 HCFC141b 0.14 HFC245fa ~0.15 CO2 0.24

Optimal Foam k-Factors Thickness @ equal insulation CFC-11 0.11 1.0 HCFC141b 0.14 1.3 HFC245fa ~0.15 1.4 CO2 0.24 2.2 Change from CFC to HCFC to HFC has resulted in diminished efficiency !

Why MF best Choice? Not Petrochemical dependant CH3OH + CO → CH3OOCH Carbonylation of methanol w alkoxide cat. CH3OH + CO → CH3OOCH A more stable price than HCs

Why MF best Choice? Not Petrochemical dependant A Most Efficient BA

Side–by-Side Trials Equivalent insulation to: HFC-134a HFC-245fa HCFC-22 Trialed & Commercialized In: Drink Dispensers, Vendor Cabinets, Display Cases

Lead Candidates after HFCs MOST EFFICIENT Less Required Lower BP better Lower λ better Better solubility MF n-C5 c-C5 Mol Wt 60 72 70 BP C 32 37 49 Lambda 10.7 14 11 Solubility XLNT POOR FAIR

Why MF best Choice? Not Petrochemical dependant A Most Efficient BA Least Flammable of lead candidates

MF Least Flammable MF nC5 cC5 Flash Point, ºC -32 -40 -37 FP higher

MF Least Flammable MF nC5 cC5 Flash Point, ºC FP higher LFL, % v/v 5 -32 -40 -37 FP higher LFL, % v/v 5 1.4 1.1 LFL greater

MF Least Flammable MF nC5 cC5 Flash Point, ºC FP higher LFL, % v/v -32 -40 -37 FP higher LFL, % v/v 5 1.4 1.1 LFL greater Ht of Combust,* KJ/g -16.2 -49.7 -46.9 HOC lower * MeOH = -23.8 KJ/g

MF Least Flammable MF nC5 cC5 Flash Point, ºC FP higher LFL, % v/v -32 -40 -37 FP higher LFL, % v/v 5 1.4 1.1 LFL greater Ht of Combust,* KJ/g -16.2 -49.7 -46.9 HOC lower extra FRA Req’d 15-30% No Load * MeOH = -23.8 KJ/g

Why MF best Choice? Not Petrochemical dependant A Most Efficient BA Least Flammable of lead candidates Environmentally benign

MF and the Environment Zero ODP Very low GWP Thank You !

Effect on Global Warming Blowing Agent Molecular Weight MF 60 HCFC-141b 117 HCFC-142b 100.5 HCFC-22 86.5 HFC-134a 102 HFC-245fa 134 HFC-365mfc 148 Better solubility than nC5 !

Effect on Global Warming Blowing Agent Molecular Weight Weight Ratio MF 60 1.00 HCFC-141b 117 1.95 HCFC-142b 100.5 1.68 HCFC-22 86.5 1.44 HFC-134a 102 1.70 HFC-245fa 134 2.23 HFC-365mfc 148 2.47 Better solubility than nC5 !

Effect on Global Warming Blowing Agent Molecular Weight Weight Ratio GWP-100 MF 60 1.00 HCFC-141b 117 1.95 725 HCFC-142b 100.5 1.68 2310 HCFC-22 86.5 1.44 1810 HFC-134a 102 1.70 1430 HFC-245fa 134 2.23 1030 HFC-365mfc 148 2.47 794 Better solubility than nC5 !

Effect on Global Warming Blowing Agent Molecular Weight Weight Ratio GWP-100 Relative GWP * MF 60 1.00 HCFC-141b 117 1.95 725 1414 HCFC-22 86.5 1.44 1810 2609 HFC-134a 102 1.70 1430 2431 HFC-245fa 134 2.23 1030 2300 HFC-365mfc 148 2.47 794 1959 Better solubility than nC5 ! * Lbs CO2e saved / Lb MF used

Photochemical Reactivity Maximum Incremental Reactivity Organic Compound US EPA VOC exempt MIR Values n-Pentane NO 1.54 MF Yes 0.06 Methyl Acetate 0.07 Ethane 0.31 Acetone 0.43 Better solubility than nC5 ! Ecomate® (methyl formate) has lower reactivity than some exempt compounds

MF and the Environment Zero ODP Very low GWP Save 1 metric tonne CO2e for every pound MF used Low Photochemical Reactivity (MIR) VOC Exempt by US EPA Lower emissions during processing MF requires less molar equivalents than other blowing agents – 8 yrs experience. Low environmental impact at end of life Thank You !

AHAM Refrigerator Recycle Study 8 units, 4 Mfgrs, 15-20 yrs old “All” of Blowing Agent Still in Refrigerator 25% of Blowing Agent Release during Shredding CFCs and HCFCs Degrade in Landfill HFCs Do Not Degrade in Landfill J. Air & Waste Manage. Assoc. 57:1452–1460 (2007)

Legacy Foam Recovery & Destruction Program CA Global Warming Solutions Act of 2006 (AB 32) Refrigerators, Freezers, & Buildings Mandates Recovery and Destruction of high GWP GHG foams at EOL www.arb.ca.gov/cc/foam/foam.htm

Conclusion: Why MF best Choice? Not Petrochemical dependant A Most Efficient BA Least Flammable of lead candidates Environmentally benign Save 1 MT CO2e / Lb MF used Commercially Viable – since 2000

Thank you!