Formacel and Low GWP Foam Expansion Agent - Chemours · and Low GWP Foam Expansion Agent September...
Transcript of Formacel and Low GWP Foam Expansion Agent - Chemours · and Low GWP Foam Expansion Agent September...
Polyurethanes 2012 Technical Conference
Atlanta, Georgia
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
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Outline
• Program status and customer feedback
• Customer evaluation: Formacel® 1100 vs HFC(245fa / 365mfc) blends
• Lab study: Formacel® 1100 level optimization
• Summary
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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
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General Customer Feedback
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…)
HCFC-141b
(CCl2FCH3)
HFC-245fa
(CF3CH2CHF2)
CFC-11
(CFCl3)
Formacel® 1100
(CF3CH=CHCF3)
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Formacel® 1100 – Excellent Environmental Profile
• ODP : 0
• GWP 100 yr ITH : 8.9 (NOAA)
• Atmosphere Lifetime: 22 days (NOAA)
• VOC: None*
CF3CH=CHCF3*Expected based on low MIR or POCP value
Foam Expansion Agent MIR (g O3/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
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Formacel® 1100 vs Other Zero ODP Options
[1] Based on low MIR number
[2] AEL is DuPont Allowable Exposure Limits (8-12 hr TWA)
PropertyFormacel®
1100HFC-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 oC (mW/mK)
10.7 12.7 10.5 13 10.7
Boiling Point (oC) 33 15 40 49 32
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 .
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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
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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
* Based on low MIR value
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
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Customer Evaluation - Pour-in-Place (PIP) Formulation
Formulation70:30 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
Equal molar drop-in to the existing 70:30 HFC(245fa:365mfc) PIP formulation
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Chemical & Physical Stability – PIP Formulation
Stability Initial 1 months 3 months
Physical StabilitySoluble
(same as HFC)
Soluble
(same as HFC)
Soluble
(same as HFC)
Chemical Stability
Cream time (second) 20 20 18
Gel time (second) 87 86 81
Tack free (second) 125 124 117
Density (kg/m3) 29.2 28.9 28.2
Formacel® 1100 showed good stability in HFC(365mfc/245fa) formulation
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Foam Properties - PIP Formulation
Foam Property 70:30 HFC
(245fa:365mfc) BlendFormacel® 1100
Density (kg/cm3) 27.0 27.9
Initial k-factor (mW/mK at 23 oC) 23.7 22.1
Compressive Strength (N/cm2) 15.5 14.0
Dimensional Stability (Volume %)
Cold ( -20 oC /72 h) -0.7 -1.3
Hot (100 oC/72 h) 5.8 6
Hot & Humid (100 oC/95% RH/72 h) -0.6 -0.9
Formacel® 1100 foam showed 7% improved k-factor.
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Customer Evaluation - Spray Foam Formulation (k-factor & Density)
Foam Property70:30 HFC
(245fa:365mfc) BlendFormacel® 1100
Core Density (kg/m3) 36.0 35.3
k-factor at 23 oC (mW/mK) 21.6 20.2
k-factor at 23 oC (mW/mK) - after 1 day 21.7 20.2
Closed cell % 93% 95%
• 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
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Customer Evaluation – Spray Foam (Other Foam Properties)
Foam Property
70:30 HFC
(245fa:365mfc)
Blend
Formacel® 1100
Dimensional Stability (% Volume change)
Cold(-30 oC/48 h) – parallel -0.38% -0.72%
Cold(-30 oC/48 h) – perpendicular -5.94% -6.99%
Hot(70 oC/48 h) – parallel 0.10% -0.26%
Hot(70 oC/48 h) – perpendicular -2.59% -0.95%
Hot Humid (70 oC/95% RH/48 h) - parallel -0.1% 1.2%
Hot Humid (70 oC/95% RH/48 h) - perpendicular 4.76% 6.98%
Mechanical Properties
Compressive strength -parallel (kPa) 181 187
Bending strength (kPa) 155 163
• Formacel® 1100 showed comparable other foam properties
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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
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Recent Lab study - Formacel® 1100 vs HCFC-141b
* Expected based on low MIR value
FEA Property HCFC-141b Formacel® 1100
Molecule Structure CCl2FCH3 CF3CH=CHCF3
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 oC (mW/mK) 9.7 10.7
Boiling Point (oC) 32 33
Molecular Weight 117 164
Formacel® 1100 - a zero ODP and low GWP version of HCFC-141b
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Formacel® 1100 Level Reduction
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%
• Generic appliance formulation
• Formacel® 1100 level reduction from 73 mole% to 40 mole%
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Impact of Formacel® 1100 Level Reduction
Initial Foam Properties73 mole %
Formacel®
1100
40 mole %
Formacel®
1100
Density(kg/m3) 27.0 28.5
k-factor(mW/mK) at 24 oC 20.3 20.3
k-factor (mW/mK) at 10 oC 19.9 19.4
k-factor (mW/mK) at 1.7 oC 20.0 19.2
Relative k-factor changes
k-factor at 24 oC Control 0.0%
k-factor at 10 oC Control -2.3%
k-factor at 1.7 oC Control -4.1%
Relative FEA changes
FEA (weight) Control -45%
At 40 mole% Formacel® 1100:
� Reduced FEA usage by 45 wt%
� Improved k-factor at 10Co and 1.7Co
� No impact on k-factor at 24Co
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HCFC-141b Level Reduction
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%
• Same generic appliance formulation
• Reduced HFC-141b level from 73 mole% to 40 mole%
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Impact of HCFC-141b Level Reduction
Initial Foam Properties73 mole %
HCFC-141b
40 mole %
HCFC-141b
Density (kg/m3) 28.8 28.2
k-factor (mW/mK) at 24 oC 20.1 21.1
k-factor (mW/mK) at 10 oC 19.5 20.1
k-factor (mW/mK) at 1.7 oC 19.3 19.7
Relative k-factor changes
k-factor at 24 oC Control 4.9%
k-factor at 10 oC Control 3.3%
k-factor at 1.7 oC Control 1.9%
Relative FEA changes
FEA (weight) Control -45%
At 40 mole% HCFC141b:
� Reduced FEA usage by 45 wt%
� Worse k-factor at all temperatures
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Comparison of Formacel® 1100 at 40 mole% vs HCFC-141b at 73 mole%
Initial Foam Properties73 mole
% HCFC-141b
40 mole %
Formacel®
1100
Density (kg/m3) 28.8 28.5
k-factor (mW/mK) at 24 oC 20.1 20.3
k-factor (mW/mK) at 10 oC 19.5 19.4
k-factor (mW/mK) at 1.7 oC 19.3 19.2
Relative k-factors
k-factor at 24 oC Control 1.0%
k-factor at 10 oC Control -0.2%
k-factor at 1.7 oC Control -0.4%
Relative FEA Changes
FEA (weight) Control -23%
• Reduced Formacel® 1100 usage by 23 wt%
• Equivalent k-factor performance at all temperatures
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Customer Data - Formacel® 1100 Level Impact (HFC-245fa Appliance Formulation)
Reduced Formacel® 1100 level showed
improved k-factor at 1.7Co with no impact
on k-factor at 24Co
75 mole %
Formacel®
1100
54 mole %
Formacel®
1100
Polyol and Additive (pbw) 100 100
Water (pbw) 1.31 2.81
FEA (pbw) 36.8 29.9
Initial Foam Properties
Density(kg/m3) 31.7 29.4
k-factor(mW/mK) at 24oC 19.3 19.3
k-factor (mW/mK) at 1.7oC 18.6 17.6
Relative k-factor Changes
k-factor(mW/mK) at 24oC Control 0.0%
k-factor (mW/mK) at 1.7oC Control -5.4%
Relative FEA Changes
FEA (weight) Control -19%
Reference: Proceedings of Polyurethanes Technical Conference (2011)
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Customer Data – HFC-245fa Level Impact (HFC-245fa Appliance Formulation)
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/m3) 31.5 28.5
k-factor (mW/mK) at 24 oC 19.6 20.2
k-factor (mW/mK) at 1.7 oC 17.0 17.4
Relative k-factor Changes
k-factor (mW/mK) at 24 oC Control 3.1%
k-factor (mW/mK) at 1.7 oC Control 2.4%
Relative FEA Changes
FEA (weight) Control -19%
Reduced HFC-245fa level showed worse k-factors at 24 Co & 1.7Co
Reference: Proceedings of Polyurethanes Technical Conference (2011)
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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
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Formacel® 1100 Level Optimization
Reference: Proceedings of Polyurethanes Technical Conference (2010 & 2011)
The different behavior (k-factor vs FEA level) of Formacel® 1100 provides
an opportunity for optimization
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DuPont Lab Study - Formacel® 1100 – Cyclopentane (Cp) blends
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
Levels of Formacel ®1100 can be adjusted using water and cyclopentane
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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)
Initial Properties
Density (kg/m3) 27.9 27.0 28.5 30.0 28.4
k-factor (mW/mK) at 24 oC 22.5 20.3 20.3 19.6 21.4
k-factor (mW/mK) at 10 oC 21.9 19.9 19.4 19.1 20.3
k-factor (mW/mK) at 1.7 oC 21.8 20.0 19.2 19.5 19.9
Relative k-factor vs Cp
k-factor (mW/mK) at 24 oC Control -10% -10% -13% -5%
k-factor (mW/mK) at 10 oC Control -9% -11% -13% -7%
k-factor (mW/mK) at 1.7 oC Control -8% -12% -10% -8%
Relative Formacel® 1100 Usage
Relative Formacel® 1100 Usage vs Equal Molar Substitution(pbw)
Control -45% -47% -61%
DuPont Lab Study - Formacel® 1100 – Cyclopentane (Cp) blends (Cont.)
Formacel® 1100 at reduced levels can provide improved insulation performance.
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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
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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.