Formacel 1100 (FEA-1100) a Zero ODP and Low GWP Foam Expansion Agent September 24-26, 2012 Gary Loh, Joseph A Creazzo, Mark L Robin Ph.D, Saadat A Ata Polyurethanes 2012 Technical Conference Atlanta, Georgia
2 Outline Program status and customer feedback Customer evaluation: Formacel 1100 vs HFC(245fa / 365mfc) blends Lab study: Formacel 1100 level optimization Summary
3 Program Status FEA-1100 is now Formacel 1100 Samples are available for customer evaluation Customer feedback from global evaluation indicates significant improvement in performance DuPont is moving forward with Formacel 1100 commercialization Regulatory approval in progress TSCA (Japan) approved REACH (Europe) approved SNAP/PMN (US) in process Pilot plant in progress Evaluating various commercial sale options targeted for 2013-2016
4 General Customer Feedback CFC-11 HCFC-141b HFC-245fa Formacel 1100 (CFCl 3 ) (CCl 2 FCH 3 ) (CF 3 CH 2 CHF 2 ) (CF 3 CH=CHCF 3 ) Chlorine High Less No No ODP High Lower No No Double bond No No No Yes GWP(100yr ith) High Less Less Low Key Criteria for New FEAs Environmental Sustainability (ODP, GWP, VOC..) Safety (Toxicity, Flammability, Pressure..) Performance (Stability, Energy Efficiency, Foam Properties..) Cost Effective (Efficiency, Compatibility, Handling )
5 Formacel 1100 Excellent Environmental Profile ODP : 0 GWP 100 yr ITH : 8.9 (NOAA) Atmosphere Lifetime: 22 days (NOAA) VOC: None* *Expected based on low MIR or POCP value CF 3 CH=CHCF 3 Foam Expansion Agent MIR (g O 3 /g) Formacel 1100 0.04 Methyl Formate 0.06 HFO-1234ze 0.1 HFO-1234yf 0.28 n-pentane 1.31 Isopentane 1.45 Cyclopentane 2.39 Ethane 0.28 Foam Expansion Agent POCP Formacel 1100 3.4 Methyl Formate 3.3 HFO-1234ze 6.4 HFO-1234yf 7.0 n-pentane 39.5 Isopentane 40.5 Ethylene 100 Ethane 12.3
6 Formacel 1100 vs Other Zero ODP Options Formacel 1100 - the only zero ODP option that also provides low GWP, non-voc, low toxicity, non-flammability, low thermal conductivity and suitable boiling point. Property Formacel 1100 HFC- 245fa HFC- 365mfc Pentanes (Cyclopentane) Methyl Formate ODP 0 0 0 0 0 GWP(100yr ITH) 8.9 1030 794 11 <25 VOC No [1] No No Yes No Toxicity OEL, TLV or AEL (ppm) 500 [2] 300 1000 600 100 Flammability No No Yes Yes Yes Lambda @ 25 o C (mw/mk) 10.7 12.7 10.5 13 10.7 Boiling Point ( o C) 33 15 40 49 32 [1] Based on low MIR number [2] AEL is DuPont Allowable Exposure Limits (8-12 hr TWA)
7 Performance Demonstration from Customer Evaluations Drop-in performance for various applications (compared to HFC-245fa) Physical stability (up to 9 months) Chemical stability (up to 9 months) Insulation performance (initial & aged k-factors) Energy efficiency (appliance test) Other foam properties (dimensional stability, mechanical properties..) Use in blends to balance insulation performance & cost
8 Recent Customer Evaluations - Formacel 1100 vs HFC(245fa:365mfc) Blend 70:30 HFC(245fa:365mfc) blend - improved flammability & vapor pressure Data from 2 customers - pour-in-place (PIP) & spray foam applications FEA Property HFC-245fa HFC-365mfc Formacel 1100 ODP 0 0 0 GWP(100yr ith) 1030 794 8.9 VOC No No No* Toxicity - TLV, OEL or AEL (ppm) 300 1000 500 Boiling Point (C) 15 40.2 33 Flammability No Yes No Lambda @ 25 C (mw/mk) 12.7 10.5 10.7 * Based on low MIR value
9 Customer Evaluation - Pour-in-Place (PIP) Formulation Equal molar drop-in to the existing 70:30 HFC(245fa:365mfc) PIP formulation Formulation 70:30 HFC (245fa:365mfc) Formacel 1100 Polyol Blend (pbw) 100 100 Additives & Flame Retardant (pbw) 24 24 Water (moles) 0.16 0.16 Foam Expansion Agent (moles) 0.22 0.22
10 Chemical & Physical Stability PIP Formulation Formacel 1100 showed good stability in HFC(365mfc/245fa) formulation Physical Stability Chemical Stability Stability Initial 1 months 3 months Soluble (same as HFC) Soluble (same as HFC) Soluble (same as HFC) Cream time (second) 20 20 18 Gel time (second) 87 86 81 Tack free (second) 125 124 117 Density (kg/m 3 ) 29.2 28.9 28.2
11 Foam Properties - PIP Formulation Formacel 1100 foam showed 7% improved k-factor. Foam Property 70:30 HFC (245fa:365mfc) Blend Formacel 1100 Density (kg/cm 3 ) 27.0 27.9 Initial k-factor (mw/mk at 23 o C) 23.7 22.1 Compressive Strength (N/cm 2 ) 15.5 14.0 Dimensional Stability (Volume %) Cold ( -20 o C /72 h) -0.7-1.3 Hot (100 o C/72 h) 5.8 6 Hot & Humid (100 o C/95% RH/72 h) -0.6-0.9
12 Customer Evaluation - Spray Foam Formulation (k-factor & Density) Equal molar drop-in to 70:30 HFC(245fa:365mfc) spray foam formulation Foam sprayed using a Graco/Gusmer FF-1600 spray machine Formacel 1100 showed 7% improved k-factor Foam Property 70:30 HFC (245fa:365mfc) Blend Formacel 1100 Core Density (kg/m 3 ) 36.0 35.3 k-factor at 23 o C (mw/mk) 21.6 20.2 k-factor at 23 o C (mw/mk) - after 1 day 21.7 20.2 Closed cell % 93% 95%
Customer Evaluation Spray Foam (Other Foam Properties) 13 Formacel 1100 showed comparable other foam properties Foam Property Dimensional Stability (% Volume change) 70:30 HFC (245fa:365mfc) Blend Formacel 1100 Cold(-30 o C/48 h) parallel -0.38% -0.72% Cold(-30 o C/48 h) perpendicular -5.94% -6.99% Hot(70 o C/48 h) parallel 0.10% -0.26% Hot(70 o C/48 h) perpendicular -2.59% -0.95% Hot Humid (70 o C/95% RH/48 h) - parallel -0.1% 1.2% Hot Humid (70 o C/95% RH/48 h) - perpendicular 4.76% 6.98% Mechanical Properties Compressive strength -parallel (kpa) 181 187 Bending strength (kpa) 155 163
14 Comparison of k-factor Improvement from Customer Evaluations Formacel 1100 showed improved k-factors in all 3 cases FEA level and B-side formulations affect the amount of improvement *Reference: Proceedings of Utech Europe 2012
15 Recent Lab study - Formacel 1100 vs HCFC-141b Formacel 1100 - a zero ODP and low GWP version of HCFC-141b FEA Property HCFC-141b Formacel 1100 Molecule Structure CCl 2 FCH 3 CF 3 CH=CHCF 3 Chlorine Yes No ODP 0.11 0 GWP (100 yr ITH) 725 8.9 VOC No No* Exposure Limits (ppm) 500 500 Flammability No No Lambda @ 25 o C (mw/mk) 9.7 10.7 Boiling Point ( o C) 32 33 Molecular Weight 117 164 * Expected based on low MIR value
Formacel 1100 Level Reduction 16 Generic appliance formulation Formacel 1100 level reduction from 73 mole% to 40 mole% Formulations 73 mole % Formacel 1100 40 mole % Formacel 1100 Foam index 1.2 1.2 Polyol Blend (pbw) 100 100 Additives (pbw) 9.9 9.9 Water (pbw) 1.7 3.8 FEA (pbw) 42 23 Moles of FEA 0.26 0.14 Moles of Water 0.09 0.21 Mole % of FEA 73% 40%
17 Impact of Formacel 1100 Level Reduction At 40 mole% Formacel 1100: Reduced FEA usage by 45 wt% Improved k-factor at 10C o and 1.7C o Initial Foam Properties 73 mole % Formacel 1100 40 mole % Formacel 1100 No impact on k-factor at 24C o Density(kg/m 3 ) 27.0 28.5 k-factor(mw/mk) at 24 o C 20.3 20.3 k-factor (mw/mk) at 10 o C 19.9 19.4 k-factor (mw/mk) at 1.7 o C 20.0 19.2 Relative k-factor changes k-factor at 24 o C Control 0.0% k-factor at 10 o C Control -2.3% k-factor at 1.7 o C Control -4.1% Relative FEA changes FEA (weight) Control -45%
18 HCFC-141b Level Reduction Same generic appliance formulation Reduced HFC-141b level from 73 mole% to 40 mole% Formulations 73 mole % HCFC-141b 40 mole % HCFC-141b Foam index 1.2 1.2 Polyol Blend (pbw) 100 100 Additives (pbw) 9.9 9.9 Water (pbw) 1.7 3.8 FEA (pbw) 30 16 Moles of FEA 0.26 0.14 Moles of Water 0.09 0.21 Mole % of FEA 73% 40%
19 Impact of HCFC-141b Level Reduction At 40 mole% HCFC141b: Reduced FEA usage by 45 wt% Worse k-factor at all temperatures Initial Foam Properties 73 mole % HCFC- 141b 40 mole % HCFC- 141b Density (kg/m 3 ) 28.8 28.2 k-factor (mw/mk) at 24 o C 20.1 21.1 k-factor (mw/mk) at 10 o C 19.5 20.1 k-factor (mw/mk) at 1.7 o C 19.3 19.7 Relative k-factor changes k-factor at 24 o C Control 4.9% k-factor at 10 o C Control 3.3% k-factor at 1.7 o C Control 1.9% Relative FEA changes FEA (weight) Control -45%
20 Comparison of Formacel 1100 at 40 mole% vs HCFC-141b at 73 mole% Reduced Formacel 1100 usage by 23 wt% Equivalent k-factor performance at all temperatures Initial Foam Properties 73 mole % HCFC- 141b 40 mole % Formacel 1100 Density (kg/m 3 ) 28.8 28.5 k-factor (mw/mk) at 24 o C 20.1 20.3 k-factor (mw/mk) at 10 o C 19.5 19.4 k-factor (mw/mk) at 1.7 o C 19.3 19.2 Relative k-factors k-factor at 24 o C Control 1.0% k-factor at 10 o C Control -0.2% k-factor at 1.7 o C Control -0.4% Relative FEA Changes FEA (weight) Control -23%
21 Customer Data - Formacel 1100 Level Impact (HFC-245fa Appliance Formulation) Reduced Formacel 1100 level showed improved k-factor at 1.7C o with no impact on k-factor at 24C o 75 mole % Formacel 1100 54 mole % Formacel 1100 Polyol and Additive (pbw) 100 100 Reference: Proceedings of Polyurethanes Technical Conference (2011) Water (pbw) 1.31 2.81 FEA (pbw) 36.8 29.9 Initial Foam Properties Density(kg/m 3 ) 31.7 29.4 k-factor(mw/mk) at 24 o C 19.3 19.3 k-factor (mw/mk) at 1.7 o C 18.6 17.6 Relative k-factor Changes k-factor(mw/mk) at 24 o C Control 0.0% k-factor (mw/mk) at 1.7 o C Control -5.4% Relative FEA Changes FEA (weight) Control -19%
Customer Data HFC-245fa Level Impact (HFC-245fa Appliance Formulation) 22 Reduced HFC-245fa level showed worse k-factors at 24 C o & 1.7C o 75 mole% HFC-245fa 54 mole% HFC-245fa Polyol and Additive (pbw) 100 100 Water (pbw) 1.28 2.75 FEA (pbw) 29.5 23.9 Initial Foam Properties Density (kg/m 3 ) 31.5 28.5 k-factor (mw/mk) at 24 o C 19.6 20.2 k-factor (mw/mk) at 1.7 o C 17.0 17.4 Relative k-factor Changes k-factor (mw/mk) at 24 o C Control 3.1% k-factor (mw/mk) at 1.7 o C Control 2.4% Relative FEA Changes FEA (weight) Control -19% Reference: Proceedings of Polyurethanes Technical Conference (2011)
23 Level Impact in Other Formulations (Formacel 1100 vs HCFC-141b) DuPont Lab Data: Equal molar substitution with 2.0-4.3% k-factor improvement Customer Data*: Equal weight substitution with 2.9-4.0% k-factor improvement Customers used less Formacel 1100 to achieve the same level of improvement * Reference: Proceedings of Utech Europe 2012
24 Formacel 1100 Level Optimization The different behavior (k-factor vs FEA level) of Formacel 1100 provides an opportunity for optimization Reference: Proceedings of Polyurethanes Technical Conference (2010 & 2011)
25 DuPont Lab Study - Formacel 1100 Cyclopentane (Cp) blends Levels of Formacel 1100 can be adjusted using water and cyclopentane Formulations (pbw) 73 mole% Cp 73 mole% Formacel 1100 40 mole% Formacel 1100 60:40 Formacel 1100:Cp blend (39 mole% Formacel 1100) 60:40 Formacel 1100:Cp blend (29 mole% Formacel 1100) Foam Index 1.2 1.2 1.2 1.2 1.2 Polyol Blend 100 100 100 100 100 Additives 9.9 9.9 9.9 9.9 9.9 Water 1.7 1.7 3.8 0.0 1.7 FEA or FEA Blends 18.0 42.1 23.0 37.4 27.4 Formacel 1100 Level 0.0 42.1 23.0 22.4 16.4
DuPont Lab Study - Formacel 1100 Cyclopentane (Cp) blends (Cont.) 26 Formacel 1100 at reduced levels can provide improved insulation performance. Initial Properties 73 mole% Cp 73 mole% Formacel 1100 40 mole% Formacel 1100 60:40 Formacel 1100:Cp blend (39 mole% Formacel 1100) 60:40 Formacel 1100:Cp blend (29 mole% Formacel 1100) Density (kg/m 3 ) 27.9 27.0 28.5 30.0 28.4 k-factor (mw/mk) at 24 o C 22.5 20.3 20.3 19.6 21.4 k-factor (mw/mk) at 10 o C 21.9 19.9 19.4 19.1 20.3 k-factor (mw/mk) at 1.7 o C 21.8 20.0 19.2 19.5 19.9 Relative k-factor vs Cp k-factor (mw/mk) at 24 o C Control -10% -10% -13% -5% k-factor (mw/mk) at 10 o C Control -9% -11% -13% -7% k-factor (mw/mk) at 1.7 o C Control -8% -12% -10% -8% Relative Formacel 1100 Usage Relative Formacel 1100 Usage vs Equal Molar Substitution(pbw) Control -45% -47% -61%
27 Summary Property data confirm that Formacel 1100 provides zero ODP and low GWP while maintaining the desired characteristics: non-voc, suitable boiling point, low vapor thermal conductivity and nonflammability Customer evaluations demonstrate that Formacel 1100 is a viable foam expansion agent for various type foams, improving performance compared to current commercial options Recent lab study and customer data show that Formacel 1100 at reduced levels can provide equivalent or improved insulation performance DuPont is conducting further studies to maximize the performance of Formacel 1100 DuPont is committed to provide an environmentally sustainable [1] FEA with significantly improved insulation performance and cost effectiveness to the foam industry DuPont is progressing toward the commercialization of Formacel 1100 [1] Environmentally sustainable is based on zero ODP, low GWP, low MIR & POCP values
28 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.