Further Development of FEA-1100: a GWP Foam Expansion Agent October 11, 2010 Gary Loh, Joseph A Creazzo & Mark L Robin Ph.D Polyurethane 2010 Technical Conference Houston Texas
2 Presentation Outline Background FEA-1100 Properties Program Status Recent study Summary
Challenges to Develop GWP FEAs 3 Reduce GWP while maintaining other desired properties DEVELOPMENT PROGRESSION FOR FLUORINATED FOAMING AGENTS HIGH ODP CFC-12 CCl 2 F 2 (-30 C) CFC-11 CCl 3 F (+24 C) Approximate boiling point shown to the right of each formula = FLAMMABLE SOME ODP HCFC-142b CClF 2 -CH 3 (-10 C) HCFC-22 CHClF 2 (-41 C) HCFC-141b CCl 2 F-CH 3 (+32 C) HCFO-1233zd CH=CHCl (+19 C) HCFO-1233xf CCl=CH 2 (+15 C) ZERO ODP HFC-134a -CFH 2 (-26 C) HFC-245fa -CH-CHF 2 (+15 C) HFC-365mfc -CH 2 - -CH 3 (+40 C) HFC-152a CH 3 -CHF 2 (-25 C) -1234ze CH=CHF (-19 C) -1234yf CF=CH 2 (-28 C) -1336mzz -CH=CH- (+33 C) FEA-1100 HIGH GWP SOME GWP LOW GWP
Selected GWP FEAs Candidates (s & HCFOs) 4 1200 Series 1300 Series 1400 Series HCFO HCFO Property 1243zf 1234yf 1234ze-E 1225ye-Z 1233xf 1233zd-Z 1345zfc 1336mzz-Z 1447fz 1438mzz-E Formula CF=CH 2 CH=CHF CF=CHF CCl=CH 2 CH=CHCl CH=CH CH=CH GWP ODP ne ne ne ne Small; disqualifie d for ODP Small; disqualified for ODP ne ne ne ne Toxicity Acceptabl e Acceptabl e Disqualifie d for toxicity Acceptable Flammability Slight Boiling Point ( C) -22-28 -19-20 14-15 19 5 32 32 29 Liquid at Room Temperature Marginal Molecular Weight 96 114 114 132 131 131 146 164 196 214
Screening GWP FEAs - ODP 5 1200 Series 1300 Series 1400 Series HCFO HCFO Property 1243zf 1234yf 1234ze-E 1225ye-Z 1233xf 1233zd-Z 1345zfc 1336mzz-Z 1447fz 1438mzz-E Formula CF=CH 2 CH=CHF CF=CHF CCl=CH 2 CH=CHCl CH=CH CH=CH GWP ODP ne ne ne ne ODP [1] ODP [1] ne ne ne ne Toxicity Acceptabl e Acceptabl e Disqualified for toxicity Acceptable Flammability Slight Boiling Point ( C) -22-28 -19-20 14-15 19 5 32 32 29 Liquid at Room Temperature Marginal Molecular Weight 96 114 114 132 131 131 146 164 196 214 1. Executive Summary: Scientific Assessment of Ozone Depletion: 2006, 19 pp. World Meteorological Organization, Geneva, Switzerland, 2007. [Reprinted from Scientific Assessment of Ozone Depletion: 2006, Global Ozone Research and Monitoring Project-Report. 50, 572 pp., World Meteorological Organization, Geneva, Switzerland, 2007.]
Screening GWP FEAs - Toxicity 6 1200 Series 1300 Series 1400 Series HCFO HCFO Property 1243zf 1234yf 1234ze-E 1225ye-Z 1233xf 1233zd-Z 1345zfc 1336mzz-Z 1447fz 1438mzz-E Formula CF=CH 2 CH=CHF CF=CHF CCl=CH 2 CH=CHCl CH=CH CH=CH GWP ODP ne ne ne ne ODP [1] ODP [1] ne ne ne ne Toxicity Acceptable Acceptable Toxicity Acceptable Flammability Slight Boiling Point ( C) -22-28 -19-20 14-15 19 5 32 32 29 Liquid at Room Temperature Marginal Molecular Weight 96 114 114 132 131 131 146 164 196 214 1. Executive Summary: Scientific Assessment of Ozone Depletion: 2006, 19 pp. World Meteorological Organization, Geneva, Switzerland, 2007. [Reprinted from Scientific Assessment of Ozone Depletion: 2006, Global Ozone Research and Monitoring Project-Report. 50, 572 pp., World Meteorological Organization, Geneva, Switzerland, 2007.]
Screening GWP FEAs - Flammability & Boiling Point 7 1200 Series 1300 Series 1400 Series HCFO HCFO Property 1243zf 1234yf 1234ze-E 1225ye-Z 1233xf 1233zd-Z 1345zfc 1336mzz-Z 1447fz 1438mzz-E Formula CF=CH 2 CH=CHF CF=CHF CCl=CH 2 CH=CHCl CH=CH CH=CH GWP ODP ne ne ne ne ODP [1] ODP [1] ne ne ne ne Toxicity Acceptable Acceptable Toxicity Acceptable Flammability Slight Boiling Point ( C) -22-28 -19-20 14-15 19 5 32 32 29 Liquid at Room Temperature Marginal Molecular Weight 96 114 114 132 131 131 146 164 196 214 1. Executive Summary: Scientific Assessment of Ozone Depletion: 2006, 19 pp. World Meteorological Organization, Geneva, Switzerland, 2007. [Reprinted from Scientific Assessment of Ozone Depletion: 2006, Global Ozone Research and Monitoring Project-Report. 50, 572 pp., World Meteorological Organization, Geneva, Switzerland, 2007.]
Screening GWP FEAs - MW 8 1200 Series 1300 Series 1400 Series HCFO HCFO Property 1243zf 1234yf 1234ze-E 1225ye-Z 1233xf 1233zd-Z 1345zfc 1336mzz-Z (FEA-1100) 1447fz 1438mzz-E Formula CF=CH 2 CH=CHF CF=CHF CCl=CH 2 CH=CHCl CH=CH CH=CH GWP ODP ne ne ne ne ODP [1] ODP [1] ne ne ne ne Toxicity Acceptable Acceptable Toxicity Acceptable Flammability Slight Boiling Point ( C) -22-28 -19-20 14-15 19 5 32 32 29 Liquid at Room Temperature Marginal Molecular Weight 96 114 114 132 131 131 146 164 196 214 1. Executive Summary: Scientific Assessment of Ozone Depletion: 2006, 19 pp. World Meteorological Organization, Geneva, Switzerland, 2007. [Reprinted from Scientific Assessment of Ozone Depletion: 2006, Global Ozone Research and Monitoring Project-Report. 50, 572 pp., World Meteorological Organization, Geneva, Switzerland, 2007.]
FEA-1100 a Sustainable & Balanced Option 9 FEA-1100 (-1336mzz) ODP = 0 GWP 100 yr ITH = 9.4 (NOAA) ATM lifetime = 24 days (NOAA) nflammable (ASTM E 681 at 60 o C & 100 o C) b.p = 33 o C CH=CH λ= 10.7 mw/mk @ 25 o C MW = 164
FEA-1100 Vapor Pressure 10 Vapor pressure well below the drum pressure rating 60 Vapor Pressure Vapor pressure (psia) 50 40 30 20 10 FEA-1100 (b.p. =33C) HCFC-141b (b.p. = 32C) HFC-245fa (b.p. = 15C) Cyclopentane (b.p. = 49C) Drum pressure rating 0 60 70 80 90 100 110 120 130 Temperature ( o F)
11 FEA-1100 Vapor Thermal Conductivity vapor thermal conductivity over broad temperature range est thermal conductivity when temperature >150F Vapor Thermal Conductivity vs Temperature Vapor thermal conductivity (Btu/hr-ft-F) 0.0160 0.0150 0.0140 0.0130 0.0120 0.0110 0.0100 0.0090 0.0080 0.0070 0.0060 0.0050 0.0040 0.0030 FEA-1100 HFC-245fa HCFC-141b Cyclopentane -50 0 50 100 150 200 250 300 Temperature ( o F)
12 DuPont GWP FEA (Blowing Agent) Program 2009 2010-2011 2012-2013 2014-2015 Screening Candidates Candidate Evaluation Customer Validation Intermediate Scale Commercial Sales Full Scale Commercial Sales Safety & Environmental Properties ODP, GWP, Flammability, Toxicity.. SNAP, PMN, REACH & additional tests as needed Launch FEA-1100 Supply FEA-1100 Desired FEA Properties Insulation performance, Stability, Solubility Support customer testing & optimization Support customer conversion Support customer conversion Manufacturability Bench scale production and optimization Small lot production Intermediate scale commercial plant Full scale commercial plant
Previous Work Demonstrating Drop-in Performance 13 Superior initial and aged K-factors than HCFC-141b, HFCs (HFC-245fa & HFC-365mfc) and pentanes (cyclopentane & isopentane) in generic formulations containing major types of polyols FEA-1100 blends improves the performance of HFCs & pentanes Good material compatibility Metal, elastomers and plastics (including ABS and HIPS) Good polyol solubility Soluble in commonly used polyols Vapor pressure at 50C is well below the drum pressure rating Reference: Proceedings of 12 th International Conference: Blowing agents and foaming processes, Cologne, Germany (2010), page 5
Recent Work Providing Data for Customer Testing 14 Further toxicity evaluation Chemical stability shelf life Thermal stability foaming process Heat of evaporation Foam expansion efficiency
Toxicity Assessment 15 Clean data so far 4-hr LC50: Skin Irritation: Ames Test: Very acute toxicity n - irritating n - mutagenic Chromosomal Aberration: genetic material damage Cardiac Sensitization: Favorable cardiac sensitization potential profile 28-Day Repeat Inhalation: Favorable repeated inhalation profile 90 Day/ developmental: Favorable repeated inhalation profile consistent with 28-day test result
Shelf Life Stability Polyether at 50 o C for 6 Months 16 FEA-1100 is stable in a generic polyether formulation after 6 month storage at 50 o C B-side ingredients Weight % (pbw) Polyether (TDA) 100 Silicon Type Surfactant 2.0 Amine-based Catalyst 3.0 Co-catalyst 1.0 Water 1.0 FEA-1100 29.4 Foam index 1.2 Days at 50 o C in Oven Cream time (seconds) Tack free (seconds) Ratio (Tack free /Cream time) Foam density (pcf) 0 25 90 3.6 2.1 4 20 90 4.5 2.2 21 21 110 5.2 2.2 53 23 100 4.3 2.4 89 25 75 3.0 2.6 122 27 120 4.4 2.6 150 28 100 3.6 2.2 187 28 100 3.6 1.9
Shelf Life Stability Polyester at 50 o C for 6 Months 17 FEA-1100 is stable in a generic polyester formulation after 6 month storage at 50 o C B-side ingredients Weight% (pbw) Aromatic Polyester 100 Silicon Type Surfactant 6.2 Potassium Catalyst 2.8 Amine-based Catalyst 0.7 FEA-1100 39.7 Foam index 2.5 Days at 50 o C in Oven Cream time (seconds) Tack free (seconds) Ratio (Tack free /Cream tim e) Foam density (pcf) 0 25 90 3.6 2.5 15 30 110 3.7 2.4 47 20 130 6.5 2.3 83 25 135 5.4 2.6 116 27 120 4.4 2.2 144 30 100 3.3 2.4 181 30 100 3.3 2.2
Thermal Stability Test - Generic Spray Foam Formulation 18 ARC test: ~90% full 120 FEA-1100 in Generic Spray Foam System 120 High FEA-1100 level Heat Wait Search cycle to 100 o C sign of decomposition Temperature (C) 110 100 90 80 70 60 50 40 Temperature Pressure 110 100 90 80 70 60 50 40 Pressure (psia) 30 30 20 20 Spay Foam Formulation Weight % pbw Polyether (Mannich-base) 50.00 Polyester 50.00 Silicone surfactant 0.25 Additive 3.00 Flame retardant (TCPP) 21.50 Tertiary amine catalyst 0.97 Potassium catalyst 0.25 Water 0.63 FEA-1100 47.69 10 0 0 0 100 200 300 400 500 600 Pressure (psia) 10 3 10 2 FEA-1100 in spray foamformulation Time (minute) Pressure vs. Temperature 10 1 0 100 200 Temperature ( o C) [Plotted as -1/T] 10
Thermal Stability Test - Generic Appliance Formulation 19 ARC test: ~90% full 120 110 FEA-1100 in Generic Appliance System 120 High FEA-1100 level 100 90 Temperature Pressure 100 80 80 Heat Wait Search cycle to 100 o C sign of decomposition Temperature (C) 70 60 50 40 30 60 40 Pressure (psia) 20 20 Appliance Formulation Weight% (pbw) Polyether (sucrose) 75.00 Polyether (TDA) 25.00 Silicone surfactant 6.00 Tertiaty amine catalyst 1 3.00 Tertiaty amine catalyst 2 0.38 Co-catalyst 0.50 Water 1.70 FEA-1100 42.05 10 0 0 0 50 100 150 200 250 300 350 400 450 500 Pressure (psia) 10 3 10 2 FEA-1100 in appliance formulation Time(minute) Pressure vs. Temperature 10 1 0 100 200 Temperature ( o C) [Plotted as -1/T]
20 Liquid Heat Capacity Liquid Heat Capacity vs. Temperature Liquid heat capacity (Btu/lb-F) 0.50 0.45 0.40 0.35 0.30 0.25 HFC-245fa HCFC-141b FEA-1100 Cyclopentane bp (F o ) 60 91 90 121 30 40 50 60 70 80 90 100 110 120 130 140 150 Temperature ( o F) FEA-1100 HFC-245fa HCFC-141b Cyclopentane
Latent Heat 21 Latent Heat vs. Temperature Latent heat(btu/lb) 200 180 160 140 120 100 80 HFC-245fa HCFC-141b FEA-1100 Cyclopentane bp (F o ) 60 91 90 121 60 30 40 50 60 70 80 90 100 110 120 130 140 150 Temperature ( o F) FEA-1100 HFC-245fa HCFC-141b Cyclopentane
22 Heat Required to Evaporate FEA-1100 Close to HCFC-141b, HFC-245fa & cyclopentane FEA-1100 HCFC-141b HFC-245fa Cyclopentane Mass Basis: Boiling point ( C) 33 32 15 49 Molecular Weight 164 117 134 70 Heat required to heat FEA from 22 C to its boiling point, (Btu/lb) 5.8 4.9 0.0 21.9 Latent heat (Btu/lb) at FEA boiling point 71.0 97.1 83.9 166.6 Total heat to vaporize FEA from 22 C, Btu/lb 76.8 102.0 83.9 188.5 Relative heat requirement to vaporize FEAs 1.00 1.33 1.09 2.46 Molar basis: Total heat to vaporize FEA from 22 C, Btu/mol 12,586 11,939 11,250 13217 Relative heat requirement to vaporize FEAs 1.00 0.95 0.89 1.05
23 Effect of FEA-1100 Level in Appliance Formulation Optimize for best insulation & FEA efficiency FEA-1100 FEA-1100 FEA-1100 (0.21 moles) (0.14 moles) (0.07 moles) Ingredients pbw pbw pbw Susrose polyol) 75 75 75 TDA 25 25 25 Surfactant 6.0 6.0 6.0 Catalyst 1 3.0 3.0 3.0 Catalyst 2 0.38 0.38 0.38 Co-catalyst 0.5 0.5 0.5 Moles of H2O 0.14 0.21 0.28 Moles of FEA-1100 0.21 0.14 0.07 Total moles of FEA-1100+H2O 0.35 0.35 0.35 Isocyanate 169 191 212 Foam index 1.1 1.1 1.1 Initial foam properties Density(pcf) 1.8 1.7 2.0 K-factor (Btu.in/ft2.h.oF) @ 35 o F 0.135 0.130 0.145 K-factor (Btu.in/ft2.h.oF) @ 50 o F 0.136 0.133 0.152 K-factor (Btu.in/ft2.h.oF) @ 75 o F 0.143 0.142 0.163 FEA-1100 pbw change 0% -34% -67% K-factor 0.165 0.155 0.145 0.135 0.125 Effect of FEA-1100 (Generic Appliance Formulation) 0.05 0.10 0.15 0.20 0.25 Moles of FEA-1100 K-factor (35F) K-factor (50F) K-factor (75F)
Effect of FEA-1100 Level in Cyclopentane 24 100 wt% FEA-1100 85 wt% FEA-1100 50 wt % FEA-1100 0 wt% FEA-1100 Incredients pbw pbw pbw pbw TDA based polyol 100 100 100 100 Surfactant 2.0 2.0 2.0 2.0 Catalyst 1.5 1.5 1.5 1.5 Co-catalyst 0.5 0.5 0.5 0.5 FEA(moles) 0.18 0.18 0.18 0.18 Water(moles) 0.056 0.056 0.056 0.056 Isocyanate 132 132 132 132 foam index 1.2 1.2 1.2 1.2 Density (PCF) 2.1 2.3 2.4 2.4 K-factor (Btu.in/ft 2.h. o F) @ 75 o F 0.138 0.137 0.148 0.151 Effect of FEA-1100 Level (Generic PIP Formulation) 0.1550 K-factor 0.1500 0.1450 0.1400 0.1350 0% 20% 40% 60% 80% 100% Weight% of FEA-1100 in cyclopentane
25 Summary Zero ODP & low GWP n-flammable FEA with boiling point close to HCFC-141b Superior insulation performance compared to HCFC-141b, HFCs (245fa & 365mfc) & pentanes (cyclopentane & Isopentane) [1] Good material compatibility and polyol solubility [1] Good chemical and thermal stability Heat of evaporation close to HCFC-141b, HFC- 245fa & cyclopentane Potential drop-in replacement with improved performance [1] Proceedings of 12 th International Conference: Blowing agents and foaming processes, Cologne, Germany (2010), page 5