UTECH 2000 Conference Paper

Additives for Pentane Lamination Rigid Foams by P. C. Hohl , J. W. Miller , A. Braun, J. Grimminger and T. Panitzsch Air Products and Chemicals, Inc.

ABSTRACT Rigid foam technology is the most dynamic segment of polyurethane chemistry today. The challenge facing rigid polyurethane manufacturers is the development of foam formulations and processing technologies that use blowing agents which are environmentally acceptable and still produce a foam that has an excellent balance of physical properties. The changes in blowing agent technologies that have been implemented over the last couple of years have resulted in numerous processing and performance issues. These issues must be resolved if polyurethane foam is to remain competitive with other insulating materials. In order to overcome many of the issues related to this change in blowing agents, formulations have been significantly modified. Fundamental changes, such as conversion from classical polyether based polyurethane to polyester based polyisocyanurate, are now considered and practiced. Currently, aliphatic hydrocarbons such as cyclo-, n- and iso-pentane are the leading class of physical blowing agents used in the European rigid foam industry. The North American lamination industry, which currently uses 141b as its blowing agent, also shows great interest in the production of hydrocarbon blown foam. After polyols, additives play the most important role in determining the final success of these blowing agent changes. This paper will discuss Air Products and Chemicals development of two new additives designed to enhance the emulsification and stabilization of pentane in rigid systems. This includes a new silicone based surfactant, Dabco DC5580, and a pentane compatibilizer and emulsifier, Dabco Kitane 20AS. Both products have been specially engineered for use in hydrocarbon blown rigid systems, allowing for higher pentane use levels and providing for wider processing latitudes. INTRODUCTION
Dabco registered trade name for Air Products and Chemicals Inc.

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Rigid polyurethane foams are commonly used in a variety of applications due to their excellent thermal and mechanical properties. The exceptional thermal properties of rigid polyurethane foam make it well known and a product of choice in both the construction and appliance industry. The ability to mold complex geometric parts featuring superior surface quality, physical properties and low raw materials usage are unique advantages associated with rigid polyurethane foams. Typical application areas for rigid polyurethane foam are: rigid bun stock or block production (construction) continuous and discontinuous lamination of insulating panels appliance industry (refrigerators, freezers) pour-in-place technology (gap filling at construction sites, pipe insulation) structural foams (computer housings, simulated wood) packaging foams

An overview of some commonly used insulating materials can be found in Table 1. This table clearly illustrates the improved physical properties offered by rigid polyurethane foam[1]. The rigid polyurethane foam industry has been affected by regulatory statutes dictating blowing agent changes. Under the Montreal Protocol, the North American and European polyurethane insulation industry will be forced to phase out HCFC-141b as a blowing agent by December 31, 2002. Table 1: Thermal conductivity of commonly used insulating materials[1] Material PUR Foam (CFC) Polystyrene Foam Rockwool Cork board Timber: white pine Density [Kg/m] 32 16 100 220 350-500 value [mW/(m*K)] 17 35 37 49 112 Thickness required for same insulation [mm] 20 44 46 61 140+

One alternative to HCFC blowing agents are aliphatic hydrocarbons. These materials include n-pentane, cyclo-pentane and iso-pentane, which are currently used as blowing agents in both Europe and Asia. When European laminators changed blowing agents to hydrocarbons a few years ago, it started also a trend to replace polyurethane (PUR) foams with polyisocyanurate (PIR) foams. PIR foams low density, superior thermal resistivity, good structural properties, excellent fire performance, and cost-effectiveness are essential for maintaining a competitive edge over alternative insulation materials.

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Formulations have required significant modification to compensate for issues associated with the introduction of these new blowing agent technologies. Besides polyols, additives play the most important role in determining the success of these blowing agent changes. Surfactant compatibility with blended resin systems differs vastly when using HFC, HCFC, CFC, or hydrocarbons (pentane isomers and their blends) as blowing agents. The physical properties of these blowing agents are also dramatically different with respect to nucleation, vaporization, and diffusivity. Each of these changes in turn affects processing parameters and finished foam properties. The solubility of non-polar aliphatic hydrocarbons is limited in most polyurethane raw materials. Even when pentane is completely soluble in the polyol-containing component , it becomes increasingly incompatible with the resulting reaction mixture as urethane, isocyanurate and/or urea products are formed[2]. The proper choice of additive can significantly improve this compatibility. In most continuous applications the hydrocarbon blowing agent is introduced in line therefore it is not necessary to have complete solubility of the hydrocarbons in the polyol. Usually the hydrocarbon blowing agent is emulsified in the polyol. Additives that can improve pentane emulsification will allow for the use of higher blowing agent use levels. This in turn permits water levels in the formulation to be decreased and in some case eliminated, while still maintaining production target densities. It is important to understand that formulation optimization through careful choice of additives can result in: wider processing latitude higher concentration of fine, closed cells maximizing thermal efficiency better emulsification to reduce pentane emissions during the foaming reaction improving foam surfaces, enhanced thermal insulation and reducing plant emissions improved trimerization kinetics due to water reduction or elimination reduced exotherm, minimizing post-blow caused by thermoplasticity effects

Surfactant Structure[4] The ability of a silicone surfactant to function as both an emulsifier of polyurethane components and as a foam cell stabilizer is dependent upon its molecular structure. A silicone surfactant is comprised of two dissimilar components: a non-polar lipophilic (hydrophobic) silicone portion and a p7olar hydrophilic polyether portion. The difference in polarity between functional groups present within the same molecule results in a organo siloxane copolymer that exhibits extremely high surface activity. The low surface tension displayed by Air Products and Chemicals, Inc. 2000

polymethylsiloxanes, coupled with their high surface activity results in low surface energies in both aqueous and organic phases. The low cohesive force of the molecules results in the lowering of a materials surface tension. This allows for the favorable orientation and packing of siloxane methyl groups at an interface. The general molecular structure for a nonhydrolyzable silicone surfactant is represented in Figure 1. In polyurethanes the silicone surfactant performs a variety of functions during the foaming process. This includes both the emulsification of reactants and the nucleation and stabilization of the developing foam. The silicone-polyether surfactant is solubilized in the polyurethane intermediates and functions as an emulsifier promoting efficient mixing. The degree to which the surfactant compatibilizes these various reactants depends upon both the relative quantities and ratios of silicone and polyether in the molecule as well as the number of ethylene and propylene oxide units present in the polyether. Increased emulsification of the reaction mixture contributes to improvements in foam flow. The surface active nature of the silicone surfactants increases the number of air nuclei mixed into the reactants (nucleation) and decreases the tendency of the gas to diffuse from larger bubbles to smaller ones. This results in a foam with finer, more uniform cells. Once air nuclei are formed in the initial foam system, the expanding cells must be stabilized until the catalysts have initiated polymerization of the cell walls and struts to provide the final matrix of the foam. The surfactant accomplishes this stabilization effect by increasing capillary flow which allows the liquid in the cell walls to draw toward the inner area of the cell (susceptible to rupture) and restore the thickness of the cell wall. The properties of the silicone surfactant copolymer can be adjusted to optimal performance by varying the following parameters of the structure found in Figure 1. polysiloxane/polyether ratio and overall copolymer molecular weight (ratio of x to y) ethylene oxide/propylene oxide ratio (EO/PO) and length of these side chains (ratio of m to n, polyether molecular weight) the number of polyether pendants attached to the silicone backbone the type of capping group (R)

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Me Me | | Me3 SiO(SiO)x (SiO)y SiMe3 | | Me (CH2)3 | O | (CH2CH2O)m | (CHCH3CH2O)n | R

Figure 1. General non-hydrolyzable silicone surfactant structure. Surfactants play a unique role in the production of hydrocarbon blown rigid lamination foam. Compared to HCFC co-blown formulations, silicone surfactants must provide for a different level and type of emulsification and stabilization throughout the entire foaming process. This paper introduces a new commercial silicone surfactant Dabco DC5580 and data discussion encompassing the role of this surfactant in both a hydrocarbonblown polyisocyanurate and polyurethane lamination formulation. Dabco Kitane 20AS a Compatibilizer/Emulsifier for Hydrocarbon Blowing Agents[3,
5]

Expanding upon our reputation for developing novel catalysts and surfactants that meet our customer needs, Air Products and Chemicals, Inc. has recently introduced a new additive technology for hydrocarbons. One of the major limitations associated with using hydrocarbons is that use levels are limited to their solubility and associated solubilities kinetics. Phase separation issues before and during the foaming reaction will give rise to density and physical property gradients within the final product. To overcome these solubility issues increased emulsification is particularly desirable in PIR applications since it would allow for the reduction or total elimination of water from the formulation. This in turn would allow for improved reaction kinetics, isocyanurate conversions, and the production of thicker laminate panels. Dabco Kitane 20AS was developed specifically for rigid foam applications where the required amount of hydrocarbon blowing agent is not completely soluble in the polyol pre-blend. It has been found to increase the solubility and emulsification of Air Products and Chemicals, Inc. 2000

hydrocarbons in both polyether and polyester polyols. As a general rule, the suggested use level of Dabco Kitane 20AS should be similar to that of the hydrocarbon concentration. The typical physical properties of Dabco Kitane 20AS are summarized in Table 2. The average viscosity and flash point values suggest that this material can be handled like a polyol. Table 2: Physical Properties of Dabco Kitane 20AS Flash Point, C (PMCC) Viscosity (25 C), mPa s Specific Gravity (25 C); g/ml Water Solubility Cloud Point , C Appearance Calculated OH number, mg KOH/g EXPERIMENTAL In what follows a direct comparison of Dabco DC5580 with Dabco DC5598 (note that Dabco DC5598 has been found to be a highly successfully silicone surfactant used in pentane blown PIR technology) and a competitive silicone surfactant have been evaluated in both a hydrocarbon-blown polyisocyanurate and polyurethane formulation. Formulations The PIR formulation (Table 3) employed was fully hydrocarbon blown. To achieve the desired density range with zero water added, 20 parts of Dabco Kitane 20AS was added to the polyol blend. Dabco Kitane 20AS is an additive which provides increased hydrocarbon solubility/emulsification in polyol pre-blends. The formulation was catalyzed with a combination of Dabco TMR-13 and Dabco K-15. Dabco TMR-13 is a balanced trimerization catalyst for rigid polyurethane foam applications. It provides excellent flowability, resulting in both good processing latitudes, improved foam properties, including enhanced isotropy and dimensional stability, and high isocyanate conversion. Dabco K-15 is a potassium octoate based trimer catalyst for improved curing performance. Finally the formulation used a typical polyester polyol and flame retardant and was blown with a 60/40 blend of cyclo-/iso-pentane which was optimized to provide for excellent values. The B3-PUR formulation (Table 4) is based on a 60/35 blend of polyether/polyester polyol. In order to compensate for the reduced pentane solubility 5 parts of Dabco Kitane > 100 1100 0.98 NA 10-14 Amber liquid with slight odor 420

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20AS was added to the polyol to help improve pentane solubility/emulsification. The PUR formulation was catalyzed with Polycat 8, a standard rigid foam catalyst, and was blown with n-pentane. Reactivity data for the PIR and PUR lamination trails can be found in Table 5, respectively. Table 3: Formulation and reactivity for PIR lamination trials Formulation Polyester Polyol (OH #240 mg KOH/g) Dabco Kitane 20AS Flame retardant (TCPP) Silicone Surfactant Dabco TMR-13 Dabco K-15 Pentane (60/40 cyclo/iso) Polymeric MDI Table 4: Formulation and reactivity for PUR lamination trials Formulation Polyether Polyol (OH#530 mg KOH/g) Polyester Polyol (OH#240 mg KOH/g) Dabco Kitane 20AS Glycerol Flame retardant (TCPP) Water Silicone Surfactant Polycat 8 n-Pentane Polymeric MDI Table 5: Reactivity data for PIR and PUR lamination trials PIR lamination trial 5 14 PUR lamination trial 10 25 parts per weight 60.0 35.0 5.0 6.5 20.0 3.5 1.5 1.2 12.0 Index 110 parts per weight 80 20 20 2 1.0 1.6 20 Index 300

Cream time String gel

[s] [s]

Polycat registered trade name of Air Products and Chemicals Inc.

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Laminator Line Procedure These experiments were conducted on a Hennecke lamination line utilizing high pressure foam equipment. Each run was performed using one of the three surfactants previously mentioned. The target free rise density was approximately 26 Kg/m3. Processing conditions for both the PIR and PUR runs are listed in Table 6. Table 6: Laminator process parameters PIR and PUR formulation Panel Thickness Line Speed Laminator Temperature Facer Material Test Procedures ### values were measured on a Lasercomp Fox 200 instrument 7 days after production. DIN 53421 standard was used for determining foam compression strengths. Both compression strengths, parallel and perpendicular to the foam rise direction, were measured. Closed cell content [%] measurements were conducted on a Beckmann air comparison pycnometer. Cell size was calculated while determining the percentage closed cells. The closed cell determination method includes a correction for the cut cells on the surface of the foam sample. The cell size was obtained by dividing the volume of cut cells by the surface area of the foam sample. Dimensional stability was determined by storing samples for 24 h at -25 C and measuring their size according to DIN 53431 standard. DIN 4102 B2 fire tests were conducted 24 h after foam preparation. Figure 2 shows the schematic set-up of the micro burner fire test equipment used in the study. [mm] [m/min] [C] 40 12 60 bitumious paper

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Holder Frame Sample

Burner Basket

Figure 2: Schematic Set-Up for B2 Fire Test The original B2 pass test criteria does not allow for exceeding 150 mm of flame height up the vertical surface of the foam sample. Five different samples cut from the same foam were used for measuring flame height in the test. The samples were burned on both sides; thus for each foam, a total of ten flame height measurements were obtained. The flame height values reported here are the average of these ten individual measurements. Note: The formulations and flammability results disclosed herein are not intended to reflect hazards presented by these or any other materials under actual fire conditions. RESULTS AND DISCUSSION The objective of this study was to evaluate the new silicone surfactant Dabco DC5580 and to understand its impact on both processing and final foam properties (thermal and mechanical) when compared with Dabco DC5598 and a competitive silicone surfactant. Tables 7 and 8 summarize the final physical properties of the PIR and PUR foams, respectively.

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Table 7: Foam physical testing results PIR formulation Closed Dim. Stab. Compression B2 Cells @ -25C Strength Flame Height* [Kg/m3] [mW/(m*K)] [mm] [%] [KPa] [cm] [%V] Competitive 34.7 23.9 0.29 97 -2 134 56 13.0 DC5598 34.8 22.9 0.32 98 -1 140 60 13.5 DC5580 34.8 20.7 0.25 97 -2 136 64 13.5 * : Average value of 10 individual measurements Table 8: Foam physical testing results PUR formulation Core Density [Kg/m3] 30.4 30.0 29.1 7-day Aged Value [mW/(m*K)] 23.1 23.8 22.0 Cell Size [mm] 0.22 0.21 0.17 Closed Cells [%] 97 98 99 Dim Stab @ -25C Compression Strength [KPa] [%V] 0.2 124 72 0.2 127 84 -0.1 133 128 Silicone Surfactant Core Density 7-day Aged Value Cell Size

Competitive DC5598 DC5580

In the PIR formulation, Dabco DC5580 provided significantly improved thermal insulation when compared to Dabco DC5598 and the competitive surfactant. This benefit has been attributed to Dabco DC5580s ability to produce a foam with a smaller cell size (0.25 mm vs. 0.32 mm). Just as importantly the Dabco DC5580 foams experienced no deterioration in dimensional stability or compression strength resulting from this reduced cell size. The use of Dabco Kitane 20AS allowed the PIR formulations to be all pentane blown (zero water) thus eliminating any possible CO2 diffusion effects. This excellent performance of Dabco DC5580 has been confirmed in a traditional polyurethane formulation. Again the thermal insulation was improved due to the reduced cell size produced by Dabco DC5580. Both dimensional stability and compression strength data showed no impact from this reduced cell size and are comparable with market standard. SUMMARY AND CONCLUSIONS The main objective of this silicone surfactant trial was to improve the values of both pentane blown PIR and traditional pentane blown PUR lamination foam without deteriorating other physical properties, such as dimensional stability. Results from this study indicate that Dabco DC5580, a new silicone surfactant, can be used as a very powerful tool in improving thermal insulation properties of Dabco Kitane 20AS modified polyisocyanurate and

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polyurethane insulation foams. The knowledge gained from this work will lend itself to Air Products and Chemicals ongoing commitment to develop surfactants which can produce a more stable polyol/pentane emulsion resulting in the manufacturing of high quality polyurethane foam products for the rigid foam industry. ACKNOWLEDGEMENTS We like to thank Dr. C. Chittolini for the use of his production line for surfactant testing and the incorporation of Dabco Kitane 20AS used as a pentane/polyol compatibilizer/emulsifier. REFERENCES 1. Woods, G. 1987. The ICI Polyurethanes Book. New York, Brisbane, Toronto, Singapore: John Wiley & Sons. 2. Grimminger, J., and Muha. K. 1993. Silicone Surfactants for Pentane Blown Rigid Foam, Proceedings of the 1993 Polyurethanes World Congress, Vancouver , p. 609. 3. Chittolini, D. 1997. Improving the Processability of Pentane Blown Polyisocyanurate Foam for Continuous Lamination, Proceedings of the 1997 Polyurethanes World Congress, Amsterdam, p. 655. 4. Frey, J. H., Grimminger J., and Stevens R. E. New Silicone Surfactants for Rigid Polyurethane Foam, Proceedings of the 1996 UTECH conference, P 57. 5. Grimminger, J. 1999. New Additive Solutions for Rigid Polyurethane and Polyisocyanurate Lamination Foams, Proceedings of the 1999 RAPRA Catalyst and Silicone Surfactant Seminar. BIOGRAPHIES Peter C. Hohl Peter joined Air Products and Chemicals, Inc. in 1993. He has since worked in various technical areas, ranging from metal based catalysis to organic surfactants and polymer latex processing/performance. Currently, his present focus is on polyurethane additives for the rigid foam industry as a Applications Engineer in the Rigid Foam TS&D group. Peter received a BS in Chemistry from Gettysburg College and a MS in Polymer Science and Engineering from Lehigh University.

John W. Miller Air Products and Chemicals, Inc. 2000

John is a Technical Group leader in Rigid Foam TS&D for Air Products and Chemicals, Inc. His responsibilities include applications development, technical service and new product development for polyurethane additives for appliance, rigid systems and lamination industries. Prior to joining Air Products and Chemicals, Inc., his professional involvement since 1984 include production of pour-in-place flexible molded seating, Class 1 high density rigid foam systems, and systems for automotive interior. John received his BS degree from Illinois Institute of Technology in Chicago, Illinois. Jobst Grimminger Jobst received his BS degree in 1983 Fachhochschule Aalen, Germany. After 8 years of experience in development and technical service support in ZELU Chemie, a system house in Germany, Jobst joined Air Products and Chemicals GmbH in Norderstedt in 1991. Mr. Grimminger has held the position of Senior Application Chemist responsible for rigid polyurethane foam additives and additives for high density molding applications for 7 years and is now Technical Manager of PUA group in Europe. Axel Braun Axel finished his education as a chemical technician in 1987 at Deutsche Babcock Anlagen AG. He has experience in both the mechanical engineering and cosmetics industries. In 1993, he joined Air Products and Chemicals GmbH, as an application technician for silicon-based release agents. Since 1996, he is working as an application technician in rigid polyurethane foam. Torsten Panitzsch Torsten received his diploma in Chemistry in 1994 and a Ph.D. in Organic Chemistry in 1998 from the University of Kiel, Germany. After working for 8 months at Beilstein, a chemical database company, he joined Air Products and Chemicals GmbH in April 1999 as application chemist and is responsible for application development and technical service for catalysts and surfactants with emphasis on supporting rigid and high density molded market segment.

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