Further Development of FEA-1100: a Low GWP Foam Expansion Agent

Transcription

1 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 2 Presentation Outline Background FEA-1100 Properties Program Status Recent study Summary

3 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

4 Selected GWP FEAs Candidates (s & HCFOs) 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) Liquid at Room Temperature Marginal Molecular Weight

5 Screening GWP FEAs - ODP 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) Liquid at Room Temperature Marginal Molecular Weight Executive Summary: Scientific Assessment of Ozone Depletion: 2006, 19 pp. World Meteorological Organization, Geneva, Switzerland, [Reprinted from Scientific Assessment of Ozone Depletion: 2006, Global Ozone Research and Monitoring Project-Report. 50, 572 pp., World Meteorological Organization, Geneva, Switzerland, 2007.]

6 Screening GWP FEAs - Toxicity 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) Liquid at Room Temperature Marginal Molecular Weight Executive Summary: Scientific Assessment of Ozone Depletion: 2006, 19 pp. World Meteorological Organization, Geneva, Switzerland, [Reprinted from Scientific Assessment of Ozone Depletion: 2006, Global Ozone Research and Monitoring Project-Report. 50, 572 pp., World Meteorological Organization, Geneva, Switzerland, 2007.]

7 Screening GWP FEAs - Flammability & Boiling Point 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) Liquid at Room Temperature Marginal Molecular Weight Executive Summary: Scientific Assessment of Ozone Depletion: 2006, 19 pp. World Meteorological Organization, Geneva, Switzerland, [Reprinted from Scientific Assessment of Ozone Depletion: 2006, Global Ozone Research and Monitoring Project-Report. 50, 572 pp., World Meteorological Organization, Geneva, Switzerland, 2007.]

8 Screening GWP FEAs - MW 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) Liquid at Room Temperature Marginal Molecular Weight Executive Summary: Scientific Assessment of Ozone Depletion: 2006, 19 pp. World Meteorological Organization, Geneva, Switzerland, [Reprinted from Scientific Assessment of Ozone Depletion: 2006, Global Ozone Research and Monitoring Project-Report. 50, 572 pp., World Meteorological Organization, Geneva, Switzerland, 2007.]

9 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= o C MW = 164

10 FEA-1100 Vapor Pressure 10 Vapor pressure well below the drum pressure rating 60 Vapor Pressure Vapor pressure (psia) FEA-1100 (b.p. =33C) HCFC-141b (b.p. = 32C) HFC-245fa (b.p. = 15C) Cyclopentane (b.p. = 49C) Drum pressure rating Temperature ( o F)

11 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) FEA-1100 HFC-245fa HCFC-141b Cyclopentane Temperature ( o F)

12 12 DuPont GWP FEA (Blowing Agent) Program 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

13 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

14 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

15 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

16 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 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)

17 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 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)

18 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) Temperature Pressure Pressure (psia) Spay Foam Formulation Weight % pbw Polyether (Mannich-base) Polyester Silicone surfactant 0.25 Additive 3.00 Flame retardant (TCPP) Tertiary amine catalyst 0.97 Potassium catalyst 0.25 Water 0.63 FEA Pressure (psia) FEA-1100 in spray foamformulation Time (minute) Pressure vs. Temperature Temperature ( o C) [Plotted as -1/T] 10

19 Thermal Stability Test - Generic Appliance Formulation 19 ARC test: ~90% full FEA-1100 in Generic Appliance System 120 High FEA-1100 level Temperature Pressure Heat Wait Search cycle to 100 o C sign of decomposition Temperature (C) Pressure (psia) Appliance Formulation Weight% (pbw) Polyether (sucrose) Polyether (TDA) Silicone surfactant 6.00 Tertiaty amine catalyst Tertiaty amine catalyst Co-catalyst 0.50 Water 1.70 FEA Pressure (psia) FEA-1100 in appliance formulation Time(minute) Pressure vs. Temperature Temperature ( o C) [Plotted as -1/T]

20 20 Liquid Heat Capacity Liquid Heat Capacity vs. Temperature Liquid heat capacity (Btu/lb-F) HFC-245fa HCFC-141b FEA-1100 Cyclopentane bp (F o ) Temperature ( o F) FEA-1100 HFC-245fa HCFC-141b Cyclopentane

21 Latent Heat 21 Latent Heat vs. Temperature Latent heat(btu/lb) HFC-245fa HCFC-141b FEA-1100 Cyclopentane bp (F o ) Temperature ( o F) FEA-1100 HFC-245fa HCFC-141b Cyclopentane

22 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) Molecular Weight Heat required to heat FEA from 22 C to its boiling point, (Btu/lb) Latent heat (Btu/lb) at FEA boiling point Total heat to vaporize FEA from 22 C, Btu/lb Relative heat requirement to vaporize FEAs Molar basis: Total heat to vaporize FEA from 22 C, Btu/mol 12,586 11,939 11, Relative heat requirement to vaporize FEAs

23 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) TDA Surfactant Catalyst Catalyst Co-catalyst Moles of H2O Moles of FEA Total moles of FEA-1100+H2O Isocyanate Foam index Initial foam properties Density(pcf) K-factor 35 o F K-factor 50 o F K-factor 75 o F FEA-1100 pbw change 0% -34% -67% K-factor Effect of FEA-1100 (Generic Appliance Formulation) Moles of FEA-1100 K-factor (35F) K-factor (50F) K-factor (75F)

24 Effect of FEA-1100 Level in Cyclopentane wt% FEA wt% FEA wt % FEA wt% FEA-1100 Incredients pbw pbw pbw pbw TDA based polyol Surfactant Catalyst Co-catalyst FEA(moles) Water(moles) Isocyanate foam index Density (PCF) K-factor (Btu.in/ft 2.h. o 75 o F Effect of FEA-1100 Level (Generic PIP Formulation) K-factor % 20% 40% 60% 80% 100% Weight% of FEA-1100 in cyclopentane

25 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