DuPont FEA-1100: Zero ODP, Low GWP, Non-Flammable Alternative for HCFC-141b. Helen Walter-Terrinoni Nov 12, 2010

Transcription

1 DuPont FEA-1100: Zero ODP, Low GWP, Non-Flammable Alternative for HCFC-141b Helen Walter-Terrinoni Nov 12, 2010

2 Desired Properties for HCFC-141b Phase-out 2 Environmentally sustainable Zero ODP & Low GWP Safety & Handling Low Toxicity Chemical stable Non-flammable Suitable boiling point (25C - 35C) Good insulation performance Low vapor thermal conductivity or Lambda Flexibility to use high level of FEA Low conversion cost Potential drop-in to existing process & equipment Potential drop-in to existing formulations

3 HCFC-141b Phase-out Options 3 HIGH ODP LOW ODP ZERO ODP Next Generation Low GWP Zero ODP CFC-11 HCFC-141b HFC-245fa HFC-365mfc FEA-1100 Pentanes Methyl Formate Methylal Next Generation Low GWP H2O(CO2) Mixtures HBA-2 AFA-L1

4 FEA-1100 a Sustainable & Balanced Option 4 FEA-1100 (HFO-1336mzz) ODP = 0 GWP 100 yr ITH = 9.4 (NOAA) ATM lifetime = 24 days (NOAA) Nonflammable (ASTM E 681 at 60 o C & 100 o C) b.p = 33 o C CF 3 CH=CHCF 3 = o C MW = 164

5 Challenges to Develop Low GWP FEAs 5 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 CF 3 CH=CHCl (+19 C) HCFO-1233xf CF 3 CCl=CH 2 (+15 C) ZERO ODP HFC-134a CF 3 -CFH 2 (-26 C) HFC-245fa CF 3 -CH-CHF 2 (+15 C) HFC-365mfc CF 3 -CH 2 -CF 2 -CH 3 (+40 C) HFC-152a CH 3 -CHF 2 (-25 C) HFO-1234ze CF 3 CH=CHF (-19 C) HFO-1234yf CF 3 CF=CH 2 (-28 C) HFO-1336mzz CF 3 -CH=CH-CF 3 (+33 C) FEA-1100 HIGH GWP SOME GWP LOW GWP

6 6 Foam Expansion Agent Property Comparison Property HFO 1243zf HFO 1234yf 3-Carbon Series 4-Carbon Series 5-Carbon Series HFO 1234ze-E HFO 1225ye-Z HCFO 1233xf HCFO 1233zd-Z HFO 1345zfc HFO 1336mzz-Z HFO 1447fz HFO 1438mzz-E Formula CF 3CH=CH 2 CF 3CF=CH 2 CF 3CH=CHF CF 3CF=CHF CF 3CCl= CH 2 CF 3CH=CHCl CF 3CF 2CH=CH 2 CF 3CH=CHCF 3 CF 3CF 2CF 2CH=CH 2 CF 3CH=CHCF 2CF 3 ODP None None None None Small; disqualified for ODP Small; disqualified for ODP None None None None GWP Low Low Low Low Low Low Low Low Low Low Boiling Point ( C) Liquid at Room Temperature Molecular Weight No No No No No Marginal No Yes Yes Yes Toxicity Acceptable Acceptable Disqualified for toxicity Acceptable Flammability Yes Slight No No No No

7 7 HCFC-141b Phase-out Option Comparisons FEA-1100 a zero ODP & low GWP FEA with desired properties FEAs ODP GWP Flash Point( o C) 25 o C (mw/mk) Boiling Point ( o C) Conversion Cost HCFC-141b a none NA HFC-245fa a none Med ium (High vapor pressure) HFC-365mfc a High (Flammability) Cyclopentane 0 11 b b 49 High (Flammability) CO2 0 0 none 16.3 b -139 Low Methylal High (Flammability) Methyl Formate b 32 High (Flammability) HBA-2 Negligible b <15 d none d (Potential high vapor Low - Medium pressure) AFA-L1 Negligible b <15 d none 10 b d (Potential high vapor Low - Medium pressure) FEA c none Low a: IPCC/TE AP (2005) b: UNDP, Phaseout Technologies f or PU Foams, June 2010; c: NOAA(2010) d: Proceedings of Polyureth anes 2009 Technical Conference

8 Thermal Conductivity and Vapor Pressure Comparisons 8 Low vapor thermal conductivity over broad temperature range Lowest thermal conductivity when temperature >150F Vapor thermal conductivity (Btu/hr-ft-F) Vapor Thermal Conductivity vs Temperature FEA-1100 HFC-245fa HCFC-141b Cyclopentane Temperature ( o F) 60 Vapor Pressure 50 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 Vapor pressure is very close to HCFC-141b Temperature ( o F)

9 FEA-1100 vs Other Zero ODP FEAs 75F FEA-1100 HFC-245fa PUR Foam R-value Comparisons (Equi-molar FEA) HFC-365mfc Cyclopentane Isopentane Methyl formate Methylal Ingredients pbw TDA-based polyol 100 Surfactant 2.13 Catalysts 2.00 FEAs (moles) 0.18 Water (moles) 0.06 Is ocyanate 132 Foam index FEAs R-value Density (ft 2.h. o o F (pcf) FEA HFC-245fa HFC-365mfc Cyclopentane Isopentane Methyl formate Methylal FEA-1100 has the best insulation performance

10 FEA-1100 Impact on FEA Mixtures 10 Effect of FEA-1100 on Other FEAs R-value HFC-245fa & its FEA-1100 mixture HFC-365mfc & its FEA-1100 mixture Cyclopentane & its FEA-1100 mixture Isopentane & its FEA-1100 mixture Methyl formate & its FEA-1100 mixture Methylal & its FEA-1100 mixture Other FEAs FEA-1100-other FEA mixtures FEAs R-value (ft 2.h. o 75 o F Density (pcf) Benefits HFC-245fa FEA-1100/HFC-245fa mixture Improved GWP, b.p & R-value HFC-365mfc FEA-1100/HFC-365mfc mixture Improved GWP, R-value & flammability Cyclopentane FEA-1100/cyclopentane mixture Improved R-value & flammability Isopentane FEA-1100/isopentane mixture Improved R-value & flammability Methyl formate FEA-1100/methyl formate mixture Improved R-value & flammability Methylal FEA-1100/methylal mixture Improved R-value & flammability Adding FEA-1100 to other zero ODP FEAs Same foam formulation & equi-molar FEAs FEA-1100 improves R- value

11 FEA-1100 Mixture Polyester Polyol Blend FEA-1100 to 50/50 cyclopentane(c-c5)-isopentane(i-c5) mixture Same foam formulation & equi-molar FEAs FEA-1100 improves performance Aged R-value - PIR Foam s (FEA-1100 vs 50/50 cyclopentane/isopentane) R-value Days

12 FEA-1100 vs HCFC-141b & HFCs 12 Superior insulation performance compared to HCFC-141b & HFCs Ingredients (pbw) FEA-1100 HCFC-141b HFC-245fa HFC-365mfc Sucrose- based polyol Surfactant Catalysts water (moles) FEA (moles) Isocyanate Foam Index Reaction Profile Cream time(s) Rise time(s) Tack free time(s) Foam Initial Properties Foam density(pcf) R-value (ft 2. h. o 75 o F

13 FEA Level & R-value (FEA-1100 vs HFC-245fa) 13 R-value R-value Comparison (FEA-1100 vs HFC-245fa) * High level of HFC-245fa may cause pressure exceed drum pressure rating LowFEAlevel HighFEAlevel (b.p>25c) HFC-245fa vs FEA-1100 HFC-245fa FEA-1100 High level of FEA-1100 can be used without vapor pressure or flammability limitation High level of FEA-1100 can potentially improve insulation performance HFC-245fa (low FEA level) FE A (low FEA level) Ingredients (pbw) Mannich polyol Polyester polyol Surfactant Flam e retardant and additives Catalysts FEA (moles) W ater (m oles) Isocyanate Foam index HFC-245 fa (high FEA level)* FEA-1100 (high FEA level) Reaction Profile Cream time(s) Rise time (s) Tack free time (s) Foam Initia l propertie s Sam ple density (pcf) R-value (ft 2.h. o 75 o F

14 Chemical Stability Polyether at 50 o C for 6 months 14 FEA-1100 is stable in a generic polyether formulation after 6 months storage at 50 o C B-side ingredients 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)

15 15 Chemical Stability Polyester at 50 o C for 6 months FEA-1100 is stable in a generic polyester formulation after 6 months storage at 50 o C B-side ingredients 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 time) Foam density (pcf)

16 16 Polyol Solubility FEA-1100 is soluble in commonly used polyols Polyol Type OH# (mg KOH/g) Weight% in Polyols for Single Phase Mixture (21 o C) Weight% in Polyols for Single Phase Mixture (50 o C) Polyethers Amine Sucrose/amine Sucrose/glycol Sucrose/glycerine Sorbitol Mannich-base Polyesters

17 Material Compatibility - Metal 17 FEA-1100 is compatible with commonly used metals Changes after 2 weeks at 100 o C (212 o F) in FEA-1100 Metal Coupons Metal Coupon Weight Metal Coupon Appearance FEA Solution Appearance FEA Solution Analysis Stainless Steel No weight change No sign of corrosion Clear No fluoride detected ** Carbon Steel No weight change No sign of corrosion Clear No fluoride detected ** Copper No weight change No sign of corrosion Clear No fluoride detected ** Brass No weight change No sign of corrosion Clear No fluoride detected ** Aluminum No weight change No sign of corrosion Clear No fluoride detected ** ** Detection limit = 0.5 ppm

18 18 Material Compatibility - Elastomers FEA-1100 is compatible with commonly used elastomers Changes after 2 weeks at room temperature in FEA-1100 Symbol Material Brand NR Natural Rubber Natural Rubber CR Polychloroprene Neoprene W NBR Acrylonitrile Butadiene BUNA N CSM Chlorosulfonated Polyethylene Hypalon 40 FFKM Fluoroelastomer Kalrez T Polysulfide THIOKOL FA IIR Isobutylene Isoprene Butyl Rubber EPDM Hydrocarbon (Ethylene-Propylene Terpolymer) Nordel % Weight Change % Volume Change % Hardness Change 4.4% 1.9% 0.0% 0.8% 0.1% 0.0% 15.3% 2.6% -13.6% 0.2% 0.8% -1.3% 7.9% -3.4% -2.9% 0.3% 6.7% -6.1% 0.3% 13.1% -13.3% 1.4% 5.5% -7.1%

19 Material Compatibility - Plastics FEA-1100 is compatible with commonly used plastics 19 Changes after 2 weeks at room temperature in FEA-1100 Symbol Material Brand % Weight Change % Volume Change % Hardness Change ABS Acrylonitrile-butadiene-styrene Cycolac EX58-0.1% -0.6% 0.0% HIPS High Impact Polystyrene 0.3% -0.4% -2.9% PET Poly(ethylene terephthalate) Rynite 0.0% 0.7% -1.2% PS Polystyrene Styron -0.4% 0.9% 0.0% PVC Polyvinyl Choloride Bakelite 0.0% 0.0% 0.0% CPVC Chlorinated Polyvinyl Choloride 0.0% -0.3% 0.0% PTFE Fluorocabon(PT FE) Teflon 1.1% 0.3% -17.2% ETFE Fluorocabon(ET FE) Tefzel 0.7% 0.0% 12.9% Ionomer Surlyn 0.3% 0.0% 1.9% POM Acetal Delrin 0.1% -1.2% -1.3% PC Polycarbonate Tuffak 0.0% -0.6% 0.0% PEEK Polyetheretherketone Victrex 0.0% 0.2% 0.0% Polyarylate Arylon 0.2% -0.2% -4.4% LCP Polyester Xydar 0.0% -0.4% -1.5% Nylon 6/6 Zytel % -0.5% 3.1% PEI Polyetherimide Ultem -0.1% 0.0% 0.0% Polyaryl sulfone Radel -0.2% 0.3% 0.0% PVDF Poly(vinylidene fluoride) Kynar 0.1% -0.3% 0.0% PP Polypropylene Tenite 0.3% -0.5% 0.0% LCP Zenite -0.1% -0.9% 0.0% HDPE High Density Polyethylene Alathon 0.0% 0.3% 3.3% Phenolic Duzez 0.0% -0.1% 1.2%

20 Toxicity Assessment 20 FEA-1100: Favorable Results 4-hr LC50: Skin Irritation: Ames Test: Very Low acute toxicity Non - irritating Non - mutagenic Chromosomal Aberration: No 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

21 21 DuPont Low 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

22 22 FEA-1100 Summary Zero ODP & low GWP Non-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 [2] Heat of evaporation close to HCFC-141b, HFC- 245fa & cyclopentane [2] Potential drop-in replacement with improved performance [1] Proceedings of 12 th International Conference: Blowing agents and foaming processes, Cologne, Germany (2010), page 5 [2] Proceedings of Polyurethans 2010 Technicla Conference 2010, Houston, USA (2010)

23 23 Disclaimer: The information set forth herein is furnished free of charge and based on technical data that DuPont believes to be reliable. It is intended for use by persons having technical skill, at their own risk. Since conditions of use are outside our control, we make no warranties, expressed or implied and assume no liability in connection with any use of this information. Nothing herein is to be taken as a license to operate under, or a recommendation to infringe any patents or patent applications.

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