Formacel 1100: A Zero ODP and Low GWP Foam Expansion Agent for Spray Applications. Ernest B. Wysong DuPont Chemicals & Fluoroproducts

Transcription

1 Formacel 1100: A Zero ODP and Low GWP Foam Expansion Agent for Spray Applications Ernest B. Wysong DuPont Chemicals & Fluoroproducts

2 Agenda Introduction Spray Foam Requirements Polyol Solubility Formulation / Catalyst Stability Application Behavior Physical Foam Properties Thermal Conductivity and Aging Flammability Life Cycle Analysis Conclusions Internal Use Only 2

3 Polyurethane Spray Foam Key Global Energy Trends: Energy Efficiency Minimum Environmental Footprint Sustainability One Potential Option: Spray Urethane Foam High Efficiency Enabled by Fluorochemical gases (HFCs) Current Issue: Sustainability HFCs have significant Green House Gas (GHG) footprint Internal Use Only 3

4 Formacel 1100: A Next Generation Foam Expansion Agent Ozone Depletion Potential (ODP) = 0 (no chlorine) Global Warming Potential (GWP) 100 yr ITH = 8.9 (NOAA) Atmospheric lifetime = 22 days (NOAA) Nonflammable (ASTM E 681 at 60 o C & 100 o C) CF 3 CH=CHCF 3 Boiling Point = 33 o C Vapor Thermal Conductivity k= o C AEL a = 500 ppm 8hr / 12hr F F F F Maximum Incremental Reactivity (MIR) = 0.04 g O 3 /g F F a: DuPont Acceptable Exposure Limits (8-12 hr TWA) H H HFO-1336mzz-Z CFCs HCFCs HFCs HFOs Sustainability Internal Use Only 4

5 COMPARISON OF FORMACEL 1100 WITH OTHER ZERO ODP FOAM EXPANSION AGENT OPTIONS Property Formacel 1100 HCFC-141b HFC-245fa HFC-365mfc Cyclopentane Methyl Formate Molecule Structure Molecular CF 3 CH=CHCF 3 CCl 2 FCH 3 CF 3 CH 2 CHF 2 CF 3 CH 2 CF 2 CH 3 (CH 2 ) 5 CH 3 (HCOO) weight Boiling Point ( o C) ODP GWP(100yr ITH) <25 VOC No* No No No Yes No Exposure Limits (ppm) 500** Flammability No No No Yes Yes Yes Vapor Thermal 25 o C (mw/mk) *Expected based on low MIR Value ** DuPont Acceptable Exposure Limits (8-12 hr TWA) Internal Use Only 5

6 Spray Foam Expansion Agent Requirements Polyol / B-Side Solubility Formulation / Catalyst Stability Application Spray Behavior / Reactivity / Nonflammable Physical Foam Properties Thermal Conductivity Performance and Aging Impact on Foam Flammability Internal Use Only 6

7 Solubility of Formacel 1100 in Various Polyol Types Purpose: Determine solubility of Formacel 1100 in a wide range of polyols Results: Formacel 1100 demonstrates good solubility in a broad range of polyols. Polyol Type OH# (mg KOH/g) Formacel 1100 Solubility Limit (Weight %) 21 C 50 C Polyethers Amine Sucrose/amine Sucrose/Glycol Sucrose/Glycerine Sorbitol Mannich-Base Polyesters Internal Use Only 7

8 Formulation Stability Testing: Generic Foam Formulation Spray Machine Results Purpose: Compare spray application performance at equal weight loadings as a function of formulation storage time Results: Without optimization, equal weight Formacel 1100 foam has similar R- value and aged R-value as the HFC-245fa foam. Procedure: Formulation HFC-245fa FEA Polyols / Flame Ret Dabco DC Polycat Dabco T Foam Expansion Agent Water Total 100% 100% 1,2,3 Dabco and Polycat are trademarks of Air Products and Chemicals, Inc. The mass of HFC or HFO blowing agent was held constant. The density for the Formacel 1100 (FEA-1100) sample was adjusted by using water. Graco HV-R Reactor, 125F hoses, 1600 psig, AR4242 mix chamber Both systems were aged in 5 gallon pails in a controlled laboratory environment (room temp). Performance HFC-245fa initial HFC-245fa 6month FEA 1100 initial FEA month Cream Time (s) Gel Time (s) Tack Free (s) Density (kg/m 3 ) % closed cell R Value (ft 2. o F.h/BTU.in) Internal Use Only 8

9 25 o C Aging : Initial and 1 Month; HFC - 245fa vs. Formacel 1100 Results: Formacel 1100 has similar initial and 1-month aged reactivity to HFC-245fa Internal Use Only 9

10 6 Week Aging at 50 o C with Example 1 Formulation: HFC-245fa vs. Formacel 1100 Results: Formacel 1100 has similar reactivity to HFC-245fa through 6 weeks of aging Internal Use Only 10

11 Amine Catalyst Stability Testing Purpose: Determine inherent stability of Formacel 1100 with amine catalysts Procedure: Equal portions of neat blowing agent and amine catalyst were stored for 24 hours at 54 o C, followed by a 20-fold dilution in water and analysis for fluoride anion (F - ) by Ion Chromatography. Results: The data illustrates the important role chemical structure plays in defining chemical reactivity and unique stability of Formacel Stability after o C (ppm F - Detected) MDL F - = 0.60 ppm Foam Expansion Agent Catalyst A Catalyst B Catalyst C Formacel Other Halogenated Olefins Catalyst A: Glycine, N-[(2-hydroxy-5-nonylphenyl)methyl]-N-methyl-, sodium salt (1:1) N,N,N,N,N Pentamethyl-diethylenetriamine Catalyst B: Catalyst C: Phenol, 2,4,6-tris[(dimethylamino)methyl]- / Phenol, bis[(dimethylamino)methyl]- 1 WO 2012/ A2 Formacel 1100 Internal Use Only 11

12 Application Spray Studies / Performance Testing Purpose: Demonstrate Low Temperature Spray Application behavior (-5 o C) for Formacel 1100 vs. an HFC Formulation on an equal molar, non-optimized basis. Generic Spray Formulation #2 Component pbw Polyester Polyol Mannich Polyol Amine catalysts Metal catalysts Silicone Surfactants Fire retardant Water Foam expansion agent Index Operating Conditions Spray Machine Spray Booth Temperature Machinery Room Temperature Gusmer-type (FF-1600) -5 o C 15 o C Sample 1 Sample 2 Applied to slate board with a 5mm primer layer, 30 sec interval, then a 30 mm layer. Applied to plywood board with a 5mm primer layer and then two 25mm layers at 15 sec. intervals. Internal Use Only 12

13 Generic Spray Foam Formulation #2 Test Results at 5 o C Application Results: Formacel 1100 has similar reactivity to HFC Blend applied at 5 o C Foam Expansion Agent HFC Blend Formacel 1100 Spray Pattern Good Good (No difference) Gel time 11 sec 11 sec Free Foam Density 28.0 kg/m kg/m 3 Core Foam Density 33.5 kg/m kg/m 3 Compressive Strength (Horz.) MPa MPa Compressive Strength (Vert.) MPa MPa Closed Cell Content 93% 94% Dimensional Stability (5 -30 o C) -0.7 vol%, 0.4 thickness % -0.6 vol%, 0.4 thickness % Dimensional Stability (5 70 o C) 0.4 vol%, 0.5 thickness % 0.7 vol%, 0.3 thickness % Dimensional Stability (5 70 o C. 95% RH) 14.7 vol%, 1.6 thickness % 15.6 vol%, 1.0 thickness % Thermal Conductivity (23 o C) 21.0 mw/m o K 20.1 mw/m o K Moisture Permeability 1.25 ng/m.s.pa 1.34 ng/m.s.pa Internal Use Only 13

14 Generic Spray Foam Formulation #3: Application at 5 o C & 20 o C Purpose: Demonstrate Spray Application behavior at 5 o C and 20 o C for Formacel 1100 vs an HFC Formulation on an equal molar, non-optimized basis. Formulation #3 Spray Foam Formulation Testing Comparison (Initial vs 3 Month) HFC Blend Formacel Initial Solubility OK OK Reactivity CT/RT at 20 o C (sec.) 2/8 2/8 Density (kg/m 3 ) Foam appearance OK OK 20 o 3 months Solubility OK OK Spray Machine Reactivity CT/RT at 20 o C (sec.) 2/8 2/8 Density (kg/m 3 ) Foam appearance OK OK Formulation #3 Spray Foam Behavior Comparison at 5 o C and 20 o C Gusmer-FF1600 type / D gun Foam Expansion Agent HFC Blend Formacel Atmospheric Temp 5 o C 20 o C 5 o C 20 o C Reactivity/ Foam Ability OK OK OK OK Adhesion OK OK OK OK Internal Use Only 14

15 Generic Spray Foam Formulation #3: Application at 5 o C & 20 o C Summary: Formacel 1100 provides comparable application behavior and physical property performance across a wide range of temperatures Formulation #3 Spray Foam Physical Property Comparison From 20 o C Application Foam Expansion Agent HFC Blend Formacel 1100 Core Foam Density 33.4 kg/m kg/m 3 Compressive Strength (Horz.) MPa MPa Compressive Strength (Vert.) MPa MPa Dimensional Stability (2 -30 o C) -0.1 W%, -1.8 L % -0.1 W%, -4.0 L % Dimensional Stability (2 70 o C) 0.1 W%, -0.8 L % 0.1 W%, -1.3 L % Dimensional Stability (2 70 o C. 95% 0.8 W%, 1.3 L % 0.8 W%, -0.3 L % RH) Thermal Conductivity (23 o C) 21.8 mw/m o K 21.5 mw/m o K Moisture Permeability 3.9 ng/m.s.pa 3.7 ng/m.s.pa Internal Use Only 15

16 Thermal Conductivity and Foam Aging Purpose: Compare aged thermal conductivity performance (23 o C) at equal molar loadings of Formacel 1100 in Formulation #3 Foam (4 months). Results: Without optimization of formulation, equal molar Formacel 1100 has similar λ-value and aged λ-value to HFC Blend. Internal Use Only 16

17 Thermal Conductivity and Foam Aging: Multi-Year Results Purpose: Explore aged thermal conductivity performance of Formacel 1100 over several years versus an HCFC-141b based formulation. Proprietary 32 kg/m 3 (2 PCF) spray foam formulation based on Formacel 1100 as the foam expansion agent. Test initially, then at 4 years and 5 years (23 o C). Results: Formacel 1100 has excellent thermal conductivity retention vs. HCFC-141b Aged Thermal Conductivity of 32 kg/m 3 Spray Foam HCFC-141b Formacel 1100 Initial 18.5 mw/m o K 18.6 mw/m o K 4 years 26.9 mw/m o K 24.3 mw/m o K 5 years 27.1 mw/m o K 24.6 mw/m o K Internal Use Only 17

18 Flammability of Foams Purpose: Explore small scale combustion behavior of Formacel 1100 based foams: European Ignitability Test EN ISO Summary of the Ignitability test: Test specimen 250 mm long x 90 mm wide Marked from 100 mm length and ending 200 mm Burner distance = 20 mm The flame is applied for 15 seconds Record maximum flame height during the 15 second observation 150 mm (Euro class E) > 150 mm (Euro class F) Comparison of Small Burner Ignitability Testing Foam Expansion Agent HFC-365mfc /HFC-227ea Formacel 1100 Comparison of Small Scale JIS A 9511 Combustion Results Foam Expansion Agent HFC Blend Formacel 1100 Combustion Test (EN ISO ) Avg. of mm 130 mm Combustion Test (JIS A 9511) Flame Ht (mm)/ Duration (s) 37 mm / 39 sec 35 mm / 39 sec Results: Similar behavior observed for Formacel 1100 foams vs HFC formulations Internal Use Only 18

19 Flammability of Foams Purpose: Determine impact of Formacel 1100 on large scale foam flammability testing Method: ASTM E84 tunnel test (common large scale assessment) Test specimen (18 inches wide by 24 feet long) 10 minutes flame exposure Flame Spread and Smoke Developed are assessed (FSI and SDI) Compared to standards. Results: Good E84 performance with Formacel Details: Customer proprietary 32 kg/m 3 foam E84 Test Results For Formacel 1100 Spray Foam Sample Test Specimen Formacel 1100 SPF Formulation Flame Spread Index Smoke Developed Index Exterior view of the Steiner Tunnel Apparatus: Underwriters Laboratories Inc., Internal Use Only 19

20 Life Cycle Analysis Customer testing and Life Cycle Analysis (LCA) for Formacel 1100 foams show: Low Climate Change Potential Better energy efficiency Lower greenhouse gas emissions Cradle-to-Grave Climate Change Potential on an equal thickness basis. Energy savings are normalized to water/co2 blown foam, i.e. results represent incremental differences of energy savings as compared to a water/co2 blown foam baseline. Energy savings based on (a) Houston, TX (b) Baltimore, MD (c) Chicago, IL. Net CTGr CCP is tabulated. Internal Use Only 20

21 Summary Formacel 1100 provides zero ODP and low GWP while maintaining desired characteristics: non-voc, suitable boiling point, low vapor thermal conductivity and non-flammability Customer evaluations demonstrate that Formacel 1100 is a viable foam expansion agent for spray foam applications as a replacement for HFCs. Customer testing indicates some optimizations may be necessary to capture the full potential of this product. Key parameters including stability, solubility, reactivity, physical properties, aging and flammability can be met with Formacel 1100 in spray foam applications. Internal Use Only 21

22 Acknowledgement: Air Products and Chemicals Inc. Japanese Urethane Foam Association Internal Use Only 22

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. Internal Use Only 23

24 Thank You