EnovateTM 3000 Blowing Agent A Versatile and Cost Effective Blowing Agent Technology for Rigid Foam

Mary C. Bogdan, David J. Williams Honeywell, 20 Peabody St. Buffalo, N.Y. 14210 BIOGRAPHICAL NOTE Mary Bogdan is a principle scientist for Honeywell formerly AlliedSignal. She has a BS in Chemistry and an MBA. Mary has global technical service and application development responsibilities for blowing agents in the construction industry. She has worked extensively on introduction of Enovate 3000 Blowing Agent. ABSTRACT For the past eight years, AlliedSignal, now Honeywell has provided periodic technical and commercial updates on the development of Enovate 3000 Blowing Agent, Honeywells name for HFC-245fa, a zero ozone depletion potential (ODP) blowing agent for rigid polyurethane, polyisocyanurate and other insulation foams. Extensive work done by the foam industry has demonstrated that HFC-245fa based blowing agent technologies are technically suitable for nearly all rigid foam applications. In many cases, HFC-245fa technology is superior to current or other candidate zero ODP technologies. Two perceived issues that exist with HFC-245fa are its direct global warming potential (GWP) and cost. These perceptions result from considering only the properties of the blowing agent in isolation. This simplistic approach does not take into account the energy savings and cost take-outs possible by using HFC-245fa. If one considers the total system, it can be demonstrated that HFC-245fa technologies can be both environmentally and cost competitive to other blowing agent technologies. This paper reviews results of recent industry trials in several market areas and provides environmental and economic models that demonstrate the commercial attractiveness of this important blowing agent technology.

INTRODUCTION Honeywell has been dedicated to supplying blowing agents to the polyurethane foam industry for over 40 years. Per the Montreal Protocol, blowing agent technologies will transition from the use of HCFCs to zero ODP alternatives over the next several years. Each nation has an established phaseout date for HCFCs. The specific date of this transition varies from country to country. Honeywell continues to be dedicated to providing blowing agents to the polyurethane industry and has identified HFC245fa (1,1,1,3,3-pentafluoropropane) as the third generation (zero ODP) blowing agent. In the spring of 2001, Honeywell announced Enovate 3000 Blowing Agent as its new trade name for HFC-245fa. We feel that a Enovate 3000 Blowing Agent technology provides the optimum foam performance to the polyurethane foam industry. The construction of the commercial manufacturing facility in Geismar, LA. is on schedule for a mid 2002 startup. Honeywell recently published a comprehensive conversion manual to assist in the conversion from HCFC-141b to HFC-245fa. A new recently launched web site (www.enovate3000.com) contains the latest press releases, plant construction updates, and technical information on Enovate 3000 Blowing Agent. Honeywell continue to gain approvals and product registrations around the world to assure regulatory compliance. HFC-245fa is currently listed on the US EPA TSCA Inventory, the European EINECS Inventory, the Japanese MITI Inventory, the Australian Inventory of Chemical Substances (AICS), and Honeywell has received Ministerial Condition 10 801 approval in Canada.

Our most important activity has been working with industry to assist in the transition from currently used blowing agents to HFC-245fa. Honeywell is currently supplying HFC-245fa samples globally. In addition we are establishing a global supply chain process to ensure supply of commercial product around the world. Not only has Honeywells focus been on supplying material to the industry but also in assisting in the development of HFC-245fa foam technology. Using HFC-245fa opens a range of blowing agent options that allows the formulator to tailor the blowing agent for the specific needs of the application. Honeywell has focused an extensive research effort on the use of HFC-245fa blend technology to meet the diverse needs of the insulation market. For those applications where maximization of thermal efficiency is required, neat HFC-245fa or HFC-245fa with traditional levels of water can be used. In those applications where good thermal efficiency is required, but where there is a need to balance cost and performance, HFC-245fa co-blown with higher than traditional levels of water has been successfully employed. This technology also eliminates the need to spend large amounts of capital to convert foaming operations to handle flammable or gaseous blowing agents. HFC-245fa is being extensively used in spray and pour in place applications. This paper will discuss the most recent field trial information and an economic analysis of the application of this technology. In operations, where the investment to use flammable blowing agents such as hydrocarbons has already been made, using HFC-245fa as a co-blowing agent with hydrocarbons can be a very cost effective way to improve the overall performance of the foam. At very low concentrations of HFC-245fa can eliminate the condensation effect with hydrocarbon blown foams that negatively impact both foam lambda values and dimensional stability. This is also discussed in some detail in this paper. We have also dedicated resources in our labs to identify other co-blowing technologies based on HFC-245fa that will help meet the many needs of the rigid foam industry. HFC-245fa technology can be tailored to meet performance and economic needs of the polyurethane foam market. It will allow the foam manufacturer to meet a variety of market demands with a range of economically viable alternatives. OVERVIEW HFC-245fa is a non-ozone depleting compound with an acceptable global warming potential (GWP). It is not considered a volatile organic compound (VOC) in the US and has no long-lived atmospheric breakdown products. It is o o a non-flammable material with a boiling point of 15.3 C (59.5 F). A summary of these physical properties is contained in Table 1. In addition to physical testing extensive toxicity testing has been completed on HFC-245fa. Results indicate that HFC245fa is of low toxicity. Overall results from a series of genetic studies indicate that HFC-245fa is non-mutagenic. Also, it is not a teratogen. The American Industrial Hygiene Association has established a Workplace Environmental Exposure Level (WEEL) of 300 ppm. Anyone who uses or handles HFC-245fa should carefully review the MSDS and product label prior to use. Table 1: Physical Properties of HFC-245fa Molecular Formula.CF3CH2 CHF2 Vapor Pressure: (PSIA @ 68F) ..17.8 (kPa @ 20 C) ..123 Molecular Weight ..134.0 Vapor Thermal Conductivity @ 20 C 2 (BTU in / ft hr F)..0.074 (mW / m K) ..10.7 Water Solubility (in HFC-245fa) ..1600 ppm Boiling Point (F) ....59.5 (C).15.3 Flash Point * .None Liquid Density (g/cc @ 20C) .1.32 Vapor Flame Limits ** .None Freezing Point ( C) .. <-160 *Flashpoint by ASTM D 3828-87; ASTM D1310-86 **Flame Limits measured at ambient temperature and pressure using ASTM E681-85 with electrically heated match ignition, spark ignition and fused wire ignition; ambient air.

HFC-245fa is compatible with most metals, plastics and elastomers used in foam processing equipment. In many cases, foam produced with HFC-245fa can be made using existing foam-processing equipment with no modifications. The miscibility of a blowing agent in the polyol is critical in any foam application and an important part of foam processing. HFC-245fa has exhibited acceptable miscibility in a wide range of polyols and isocyanates. We continue to add information to our data in this area as customers request it. Table 2 contains the most recent information on HFC-245fa miscibility in polyols and isocyanates.
Table 2 Miscibility of HFC-245fa in Polyols @ 21 C (70 F) Polyol % Miscible Polyol POLYETHERS (Sucrose) >40.0 (Sucrose- Amine) >40 Huntsman Rubinol P 180b (Aromatic-Amine) 24.3 Huntsman Rubinol R 144b 36.8 Huntsman Rubinol R159 b (TDA) % Miscible

Huntsman Jeffol 360 a Huntsman Rubinol R 170b Huntsman Jeffol R 350Xa Dow Voranol* R-470Xa BASF Pluracol 824 c

>40 >40 21

35.4 >40 Huntsman Jeffol 490 a POLYESTER 23.3 23.0 KOSA Terate 2541d KOSA Terate 5521 d d 27.9 23.4 KOSA Terate 2541L KOSA Terate 254 d 18.8 32.3 KOSA Terate 2031 d Stepan Stepanol 2352 e 21.5 Great Lakes PHT 4 Diolf 6.2 KOSA Terate 2542 d MDI 15.0 10.0 BASF Luprinate M20S c BASF Luprinate M70R c a b Trademark of The Dow Chemical Company Trademark of Huntsman c Trademark of BASF Corportation d Trademark of KOSA e Trademark of Stepan Company f Trademark of Great Lakes Chemical Corporation

.
Note: To determine miscibility, a mixture containing 40 wt. % HFC-245fa and 60 wt.% polyol is prepared in a calibrated miscibility tube. The mixture is thoroughly mixed at an elevated temperature. The tube is then placed in a constant temperature bath for 24 hours. If separation occurs, the height of the blowing agent is measured and the amount dissolved in the polyol is calculated.

POLYOL SYSTEM OPTIMIZATION Although HFC-245fa does have the optimum combination of properties to make it the highest performance zero ODP blowing agent available or under development today, there is some concern that its relatively low boiling point will limit its usefulness. The concern is that the higher vapor pressure of HFC-245fa systems would result in the system not being able to be shipped in drums that are used today with systems containing 141b. We have done considerable development work on techniques to reduce the vapor pressure of polyol pre-blends containing HFC-245fa and have identified a number of options. The work has focused on polyol selection, the use of vapor pressure suppressants and the use of low vapor pressure co-blowing agents such as water and hydrocarbons to reduce the concentration of HFC245fa in the polyol system. For example, we have found that the selection of polyol has a profound influence on vapor pressure. This is illustrated in Figure 1. Knowing the working pressure rating of a 16 gauge drum (Note: CFC-11 drum) is 151 kpa , Figure 1 illustrates that at 50 C, some polyols, like KOSA Terate 203, will exceed the pressure rating of the drum at a concentration of 7% (wt). Other polyols, such as Huntsman Jeffol 800, Dow* Voranol 470X, Huntsman Jeffol 350X, and Oxid Terol 352, can be blended with HFC-245fa levels of 10 to 15%(wt.) before the blend exceeds the pressure

limit of the drum. Still other polyols, including Huntsman Jeffol 270 and Huntsman Jeffol 370 do not exceed the pressure limit of the drum even at levels as high as 20% or higher of HFC-245fa. In many cases, standard drums can be used with systems containing even high levels of HFC-245fa. Figure 1 Polyol Blend Vapor Pressure @ 50 C

220 Vapor Pressure, kpa

170

120

70

20 0 2 4 6 8 10 12 wt% HFC-245fa 14 16 18 20

Pressure Rating 16 Gauge Drum Huntsman Jeffol **** 800 Huntsman Jeffol**** 350X Oxid Terol*** 352 Huntsman Jeffol**** 370

KOSA Terate* 203 Dow Voranol ** 470X Alkapol SD-440 Huntsman Jeffol**** 270

Another way to reduce the vapor pressure of polyol blends is to use water as a co-blowing agent. In this study, the ratio of HFC-245fa to water was varied in a spray foam type formulation and the vapor pressure of the polyol blend measured at 21C and 54 C. The results are illustrated in Figure 2. The total moles of blowing agent were held constant, so as the water was increased, the level of HFC-245fa was proportionately decreased. The pressure rating of a 16-gauge drum was used as the maximum allowable pressure. As you can see, at more traditional water levels of zero, 0.5, and 1.0 parts, the vapor pressure of the premix exceeded the rating of the drum at about 37.8 C and above. However, at 1.5 and 2.0 parts water, the vapor pressure of the premix did NOT exceed the pressure rating of the drum at any temperature tested. This has been confirmed in spray foam field trials in North American. Figure 2 Vapor Pressure Reduction Using Water
250

Vapor Pressure (kpa)

200

150

100

50

0 21.1 Temperature C

54

Drum 16 gauge 1 pbw water

0 pbw water 1.5 pbw water

0.5 pbw water 2 pbw water

Additives have also been identified that lower the vapor pressure of polyol premixes containing HFC-245fa. Alpha methyl styrene (ams), long used as a stabilizer for fluorocarbons, has been found to be particularly effective. The results are illustrated in Figure 3. In a typical spray foam type of polyol premix, we found that as little as 0.02% ams added to the HFC-245fa in the polyol reduces the system vapor pressure by 7%. Adding 0.2% results in a 15% reduction in system vapor pressure. Significant reduction in vapor pressure can be obtained with the addition of small amounts of alpha methyl styrene. Figure 3 Vapor Pressure Reduction with AMS

Vapor Pressure (kpa)

150 145 140 135 130 125 120 115

0.00

0.02

0.20

HFC-245fa/CO2 (Water) BLEND TECHNOLOGY Technology consisting of HFC-245fa co-blown with higher than traditional levels of water has been successfully applied to several foam segments. Spray Foam For example, in the spray foam market, several field trials have been completed over the past several months that demonstrated that a blowing agent system consisting of approximately 30 to 50 mole percent HFC-245fa and the remainder water is a viable blowing agent technology for roofing and residential and commercial wall cavity spray foam. In each of these trials, it was demonstrated that this blowing agent technology can be processed with standard spray foam equipment using standard spraying techniques. In fact it can be processed with hose temperatures approximately 5 C lower than those used with HCFC-141b. Additionally, the polyol premixes can be shipped in standard drums. These trials have been run in conjunction with several major systems houses and contractors, including Resin Technologies, BASF, Gaco Western, Demilec, Corbond, and many others. In each case, no modifications to equipment, or drums were required to process the foams blown with combinations of HFC-245fa and water. To date, roof and/or wall trials have been run in all the states and Canadian Provinces listed in Table 3. Our customers have selected locations that would represent the extremes of ambient conditions that would be experienced, from the hot, dry Southwest to the damp, warm Southeast to the cool damp upper Midwest, to the cold north of Montreal in January. In all cases, the trials were successful and good quality foam was produced. Not only were the trials conducted in a number of locations but the foam was applied to a number of surfaces at a variety of different outdoor temperatures. Some of these trials were run as far back as 1997 and the roofs are still performing very well. Trial experience continues to grow daily.

Table 3 Geographic Location of Spray Foam Trial Location State/Province New York Wisconsin Minnesota Texas Louisiana Georgia California Idaho Arizona Michigan Montana Quebec Substrates Metal Deck Wood Concrete Bur Gypsum board Application Temperatures C 49 37.8 23.9 10 -3.9 -17.8

A comparison of specific details of two of the largest trials follows in Table 4. Table 4 Summary of Spray Foam Field Trial Evaluations Parameter/ System House Technology Used System Shipping Container Trial Location Equipment Foam Quality Core Density 6 Month Aged lambda value Compressive strength Foam surface Age of roofs/ Aged quality Resin Technologies HFC-245fa/CO2 (water) technology Standard 208 liter drum CA Standard used with HCFC141b systems 47.9 kg/m3 Equivalent to HCFC-141b 335kpa Smooth/ orange peel, no fisheyes >1 year/ excellent BASF HFC-245fa/CO2 (water) technology Standard 208 liter drum CA, AZ (2), GA, Standard used with HCFC-141b systems 48.1 kg/m3 Equivalent to HCFC-141b >345kpa Smooth/ orange peel, no fisheyes < 1 year

A key consideration has not only been performance and quality but also cost. The use of HFC-245fa co-blown with higher than traditional levels of water can be very cost effective. Table 6 presents an economic model that calculates the in-place cost of several spray foam systems.

Table 6 Economic Model for HFC-245fa/ CO2 (Water )Technology Based on US technology
Relative HCFC-141b HFC-245fa Cost Blowing Agent HFC-245fa water 50/50 mol ratio HFC-245fa water 30/70 mol ratio Water

Index Water, php HCFC-141b, pbw Enovate 3000, php Density (core), kg/m3 k-Factor, mW/m K (6 month) Efficiency, kg liq/kg foam % System Cost, /kg Foam Cost, /per unit area Cost per R 0 1 4

118 0.50 17.20

110 0.50 19.70

110 1.60 11.50 48.0 1.00 84 1.15 1.01 1.01

110 2.10 7.80 48.0 1.04 84 1.09 0.96 1.00

118 3.15 0.00 48.0 1.62 85 0.96 0.83 1.35

48.0 1.00 74 1.00 1.00 1.00

48.0 0.95 84 1.30 1.14 1.08

Factors such as raw material costs, foam thermal conductivity, and yields are included. These calculations show that a formulation that utilizes a 50/50 mole ratio of HFC-245fa and water has an in place cost of foam approximately equal to that of current US systems blown with HCFC-141b, even though the liquid system cost per pound is as much as 37% more expensive. This is because the yields seen with HFC-245fa blown foams are 8 to 15 % better than HCFC141b blown foams, primarily due to thinner skins, less densification at the substrate and more consistent density across the sample. Since the thermal conductivity of the HFC-245fa /CO2 (water) blown foam was found to be the same as the HCFC-141b blown foam at the standard six month aging interval, the cost per insulation value, or R, was also equal to that of HCFC-141b. With a 30/70 ratio of HFC-245fa and water, the cost effectiveness is even greater. With only a 4% penalty in thermal conductivity, equal or even lower in-place cost and cost per R can be achieved for HFC-245fa. Both of these blowing agent blends have been evaluated on full-scale roofing and wall trials with excellent results. For all these reasons, HFC-245fa is the right solution for the spray foam industry. Pour-in-Place Not only has this technology been used in spray foam applications, it has also been used in pour-in-place applications. This trial was also conducted by Resin Technologies using an HFC-245fa system identified as RT-5075. It is commercial cavity fill pour foam system. Again this system was shipped in a standard drum. The drum showed no signs of bulging and was not under excessive pressure when opened. The trial was conducted under the manufacturing conditions outlined in Table 7.

Table 7 Trial Manufacturing Conditions

Foam Machine

Gun Shot Size Substrate Foam Profile Fluid Pressure Temperature

Demold Time

Gusmer H6 (Product of the Gusmer Corporation) High Pressure 27.2 kg/ min Gusmer AR C Impingers 66 C-1-C 1.08 kg Treated Polyethylene Standard Pour Rise and Cure 9653-11032 kpa MDI: 29.4 C Resin: 29.4 C Hose: 29.4 C 16 Minutes

The foam processed well. There were no voids noted in the part molded. The physical properties of the foam are summarized in Table 8. In summary this was a successful trial. The foam systems were shipped in standard containers. The material was processed through existing equipment. The foam produced has superior physical properties in comparison to the current HCFC-141b system and had comparable lambda values to the existing HCFC-141b system.
Table 9 Generic Japanese Spray Foam System COMPONENT PBW TEROL * 80.00 POLYETHER 20.00 ADDITIVE 20.00 SURFACTANT 1.50 CAT 1 2.00 CAT 2 1.50 CAT 3 1.50 WATER 1.65 HFC-245fa 32.50 IsoLuprinate M 489** Index

Table 8: Foam Physical Properties Property Metric Core Density 35-42 kg 288 k Pa/m 2 157k Pa/m 2

Compressive (parallel) Compressive (perpendicular) Lambda Value MW/m K @ 25 C

21.3

Dimensional Stability( Vol %) Cold Temp -0.3 (-20C/28 Day) DryHeat >1.0 (70C/28 Days)

2.01

*Trademark of Oxid ** Trademark of BASF Corporation

High Index Spray Foam The Japanese spray foam market is significantly different from the North American spray foam market. The market is primarily wall insulation and construction is primarily concrete. The system is traditionally higher index than that used in the US and a lower density. In a joint research program with Oxid, we have conducted some initial evaluations of a generic Japanese spray foam formulation. It is important to note that this is not an optimized system. It represents preliminary work on this application. The generic formulation used in this study is contained in Table 9. As with any spray foam system vapor pressure of the polyol blend is important when one considers packaging and shipping of the polyol blend. Figure 4 illustrates the vapor pressure of the polyol blend at various temperatures in comparison to HFC-245fa neat and the vapor pressure limit of a 16-gauge drum.

Figure 4: Vapor Pressure vs Temperature Generic Japanese Foam Formulation 200 180 160 140 120 100 80 60 40 20 0 10 15 Temperature C 20 25

HFC-245fa system vapor pressure 16 guage drum

kpa

HFC-245fa neat

The foam was prepared using the equipment listed in Table 10.

Table 10 Japanese Spray Foam Processing Conditions Equipment Gusmer H2000 Resin:MDI pump ratio 1:1 Pressure MDI: 8963 kpa Pressure Resin:6895 kpa Hose MDI: 37.8C/ Resin: 49 C Temperatures Preheater 49 C temperature Gun Gusmer GX7 Module MDI.028/Resin.023 5 cm lifts sprayed on cardboard

Table 11: Physical Properties Japanese Spray Foam

Physical Properties Overall density, kg/m3 with skin on 3 Core density, kg/m

Data 28.7 28.7

There was no problem processing the Japanese spray foam system. The skin is a rough orange peel consistency. Photo 3 shows the pass line between passes of the foam. There is excellent interlayer adhesion on double passes. Table 11 summarizes initial test data on the foam sprayed. Figure 5 displays the initial lambda vs. temperature information on the foam.
Figure 5 Enovate 3000 /CO2 (water) 22.50 22.00 21.50 21.00 20.50 20.00 19.50 19.00 18.50 10 15 20 25 30 35 Temperature C

Lambda value mW/m.K

Although the system tested is not optimal this initial work is very encouraging. The Japanese system did process well. It did not have an extreme vapor pressure, indicating it may not require any special high-pressure packaging. The foam quality was good and the system can be processed in existing foam equipment. The use of HFC-245fa/CO2 (water) technology offers a viable, economically-sound solution to a variety of foam industry needs. HFC-245fa/hydrocarbon Blend Technology Another area where HFC-245fa co-blowing technology will find utility is in low temperature foam applications where hydrocarbon blown foam is currently being used. Hydrocarbon blowing agents are not the ideal blowing agent solution for all foam application because of their relatively high boiling point. At use temperatures of about 22C and below, pentane can condense in the foam cells, resulting in deterioration of the foams insulation and dimensional stability properties. Figure 6 is a plot of the thermal conductivity of PIR foams blown relative to HCFC-141b of HFC-245fa, a cyclopentane/isopentane blend, or isopentane at several mean temperatures. The graph illustrates that the HFC245fa blown foam, the bottom most line, has superior thermal conductivity to any of the blowing agents tested at all temperatures and showed no signs of deterioration at low temperatures due to condensation. Both foams blown with the pentanes, the upper two lines, showed poorer thermal conductivity at all temperatures, but were especially poor at mean temperatures below 22C due to condensation of the blowing agent in the cells. The use of hydrocarbons has gained acceptance in applications where flammability is not a key processing or foam quality requirement. However, with the condensation point, foam performance will be stressed at temperatures below 22 C. Investigation into improvement techniques would be a logical consideration.

Figure 6 Delta lambda value vs HCFC-141b vs Mean Foam Temperature Polyiso Insulation
0.045 0.040 0.035 0.030 0.025 0.020 0.015 0.010 0.005 0.000 -0.005 -0.010 0 5 10 15 20 25 30 35 Mean foam temperature C

Delta Lambda value vs HCFC-141b

HFC-245fa

cyclo/iso blend

isopentane

It was found that the addition of small amounts of HFC-245fa to hydrocarbon blown foams improves their low temperature thermal performance. The line, which illustrates the lambda value versus mean temperature for a foam blown with 100% isopentane, plateaus below 22C. This is a consequence of the condensation of the blowing agent in the cells. With the addition of only 2% HFC-245fa to the blowing agent, significant improvement is seen in the lambda value at all temperatures and the degree of plateauing below 22C is reduced. With the addition of 10% HFC-245fa to the blowing agent blend, further improvement in the foams lambda is seen at all temperatures and the plateauing below 22 C has almost been completely eliminated. The addition of small amounts of HFC-245fa to hydrocarbon blown foam can greatly improve the foams performance.

Figure 7 Lambda value vs Temperature vs Hydrocarbon Concentration

Lambda value mW/m K

25.5 24.5 23.5 22.5 21.5 20.5 19.5 0 10

100% Isopentane

20
Temperature C
98% Isopentane

30
90% Isopentane

40

CONCLUSION HFC-245fa is a nonflammable, non-VOC (volatile organic carbon), high performance zero ODP blowing agent. It produces foams with lambda values equivalent compared to current industry standards. The foam produced has superior lambda aging to current HCFC-141b systems. They also have superior lambda values to other alternatives at a wide range over a wide range of temperatures. HFC-245fa and HFC-245fa blend technology has been proven to work well in both field trials and lab evaluations. In conclusion, there are application specific technical and economic solutions for all major rigid foam applications utilizing HFC-245fa as a blowing agent. This paper demonstrates that the performance of HFC-245fa based coblowing agent technologies is superior to competitive technologies in almost most cases. We have demonstrated that HFC-245fa co-blowing agent technology is a viable way to achieve many of the benefits of HFC-245fa but at a reduced system cost. Honeywell will continue our development work, especially full scale trials in all rigid foam market segments. We will identify and develop other HFC-245fa based co-blowing agent technologies to meet the needs of the industry.

DISCLAIMER All statements, information and data given herein are believed to be accurate and reliable but are presented without guaranty, warranty or responsibility of any kind, expressed or implied. Statements or suggestions concerning possible use of our products are made without representation or warranty that any such use is free of patent infringement and are not recommendations to infringe any patent. The user should not assume that all safety measures are indicated, or that other measures may not be required.