ecomate Environmentally Benign Foam Blowing Agent 12 th

ecomate® Environmentally Benign Foam Blowing Agent 12 th Annual Green Chemistry & Engineering Conference 26 June 08

Need for Insulation • Saves Energy & Resources – 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 | Both multi - functional H OR

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 – Reacts with ISO → CO 2 + Polyurea • CFCs – 11 – 12 Trichloro-fluoro methane Dichloro-difluoro methane BP 23. 7 C BP -29. 8 C Dichloro-fluoro ethane Chloro-difluoro methane BP 32. 2 C BP -40. 8 C 1, 1, 1, 3, 3 Pentafluoro propane Pentafluoro butane Tetrafluoro ethane BP 15. 3 C BP 40. 2 C BP -26. 2 C ↓ • HCFCs – 141 b – 22 ↓ • HFCs – 245 fa – 365 mfc – 134 a

Blowing Agents - Environmental Characteristics • ODP – Ozone Depletion Potential • GWP – Global Warming Potential • VOC – Volatile Organic Compound ODP GWP 100 VOC

Blowing Agents - Environmental Characteristics • ODP – Ozone Depletion Potential • GWP – Global Warming Potential • VOC – Volatile Organic Compound ODP GWP 100 VOC CFC 11 1 4750 NO CFC 12 1 10, 900 NO

Blowing Agents - Environmental Characteristics ODP GWP 100 VOC CFC 11 1 4750 NO CFC 12 1 10, 900 NO HCFC 141 b 0. 1 725 NO HCFC 22 0. 05 1810 NO

Blowing Agents - Environmental Characteristics ODP GWP 100 VOC CFC 11 1 4750 NO CFC 12 1 10, 900 NO HCFC 141 b 0. 1 725 NO HCFC 22 0. 05 1810 NO HFC 134 a 0 1430 NO HFC 245 fa 0 1030 NO

Blowing Agents - Environmental Characteristics ODP GWP 100 VOC CFC 11 1 4750 NO CFC 12 1 10, 900 NO HCFC 141 b 0. 1 725 NO HCFC 22 0. 05 1810 NO HFC 134 a 0 1430 NO HFC 245 fa 0 1030 NO Cyclopentane 0 11 YES

Blowing Agents - Environmental Characteristics • MF - an attractive long term environmental option ODP GWP 100 VOC CFC 11 1 4750 NO CFC 12 1 10, 900 NO HCFC 141 b 0. 1 725 NO HCFC 22 0. 05 1810 NO HFC 134 a 0 1430 NO HFC 245 fa 0 1030 NO Cyclopentane 0 11 YES Me Formate 0 negligible NO

Ecomate® [Methyl Formate] Properties • 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 CH 3 OOCH 31. 5 ºC -32 ºC 5 - 23% 10. 7 * 586 >450 ºC 0. 982 60 * calculated

GAS LAMBDA VALUES

Optimal Foam k-Factors Optimal k-factor CFC-11 0. 11 HCFC 141 b 0. 14 HFC 245 fa ~0. 15 CO 2 0. 24

Optimal Foam k-Factors Optimal Thickness @ equal k-factor insulation CFC-11 0. 11 1. 0 HCFC 141 b 0. 14 1. 3 HFC 245 fa ~0. 15 1. 4 CO 2 0. 24 2. 2 • Change from CFC to HFC has resulted in diminished efficiency !

Why MF best Choice? • Not Petrochemical dependant – Carbonylation of methanol w alkoxide cat. CH 3 OH + CO → CH 3 OOCH – 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-134 a – HFC-245 fa – HCFC-22 • Trialed & Commercialized In: – Drink Dispensers, – Vendor Cabinets, – Display Cases

Lead Candidates after HFCs MF n-C 5 c-C 5 MOST EFFICIENT Mol Wt 60 72 70 • Less Required BP C 32 37 49 • Lower BP better Lambda 10. 7 14 11 • Lower λ better POOR FAIR • Better solubility Solubility XLNT

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

MF Least Flammable Flash Point, ºC MF n. C 5 c. C 5 -32 -40 -37 FP higher

MF Least Flammable Flash Point, ºC LFL, % v/v MF n. C 5 c. C 5 -32 -40 -37 FP higher 5 1. 4 1. 1 LFL greater

MF Least Flammable Flash Point, ºC LFL, % v/v Ht of Combust, * KJ/g * Me. OH = -23. 8 KJ/g MF n. C 5 c. C 5 -32 -40 -37 FP higher 5 1. 4 1. 1 LFL greater -16. 2 -49. 7 -46. 9 HOC lower

MF Least Flammable Flash Point, ºC LFL, % v/v Ht of Combust, * KJ/g extra FRA Req’d * Me. OH = -23. 8 KJ/g MF n. C 5 c. C 5 -32 -40 -37 FP higher 5 1. 4 1. 1 LFL greater -16. 2 -49. 7 -46. 9 HOC lower 0 15 -30% No Load

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

Effect on Global Warming Blowing Agent Molecular Weight MF 60 HCFC-141 b 117 HCFC-142 b 100. 5 HCFC-22 86. 5 HFC-134 a 102 HFC-245 fa 134 HFC-365 mfc 148

Effect on Global Warming Molecular Weight Ratio MF 60 1. 00 HCFC-141 b 117 1. 95 HCFC-142 b 100. 5 1. 68 HCFC-22 86. 5 1. 44 HFC-134 a 102 1. 70 HFC-245 fa 134 2. 23 HFC-365 mfc 148 2. 47 Blowing Agent

Effect on Global Warming Molecular Weight Ratio GWP-100 MF 60 1. 00 0 HCFC-141 b 117 1. 95 725 HCFC-142 b 100. 5 1. 68 2310 HCFC-22 86. 5 1. 44 1810 HFC-134 a 102 1. 70 1430 HFC-245 fa 134 2. 23 1030 HFC-365 mfc 148 2. 47 794 Blowing Agent

Effect on Global Warming Molecular Weight Ratio GWP-100 Relative GWP * MF 60 1. 00 0 0 HCFC-141 b 117 1. 95 725 1414 HCFC-22 86. 5 1. 44 1810 2609 HFC-134 a 102 1. 70 1430 2431 HFC-245 fa 134 2. 23 1030 2300 HFC-365 mfc 148 2. 47 794 1959 Blowing Agent * Lbs CO 2 e saved / Lb MF used

Photochemical Reactivity Maximum Incremental Reactivity US EPA VOC exempt MIR Values n-Pentane NO 1. 54 MF Yes 0. 06 Methyl Acetate Yes 0. 07 Ethane Yes 0. 31 Acetone Yes 0. 43 Organic Compound Ecomate® (methyl formate) has lower reactivity than some exempt compounds

MF and the Environment • Zero ODP • Very low GWP – Save 1 metric tonne CO 2 e 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

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. htm

Conclusion: Why MF best Choice? • • • Not Petrochemical dependant A Most Efficient BA Least Flammable of lead candidates Environmentally benign Save 1 MT CO 2 e / Lb MF used Commercially Viable – since 2000

• Thank you!