Influence of Non-Fugitive Catalysis on Physical Characteristics of Automotive Polyurethane Molded Foam

F.M. Casati, A. Fanget, J. Godoy, J.M. Sonney, R. Prange

Influence of Non-Fugitive Catalysis on Physical Characteristics of Automotive Polyurethane Molded Foam

F.M. CASATI, A. FANGET, J. GODOY, J.M. SONNEY Dow Europe GmbH International Development Center 13 rue de Veyrot P.O. Box 3 CH-1217 Meyrin 2 Switzerland ABSTRACT Traditionally, fugitive amines have been the catalysts of choice in the production of flexible molded polyurethane foams for automotive seating. Health and safety regulations, along with the continued push to eliminate VOC (Volatile Organic Compound) emissions in passenger compartments, however, are challenging the long-term use of these fugitive catalysts. Switching from conventional fugitive catalysts to non-fugitive catalysts is not trivial and many issues can arise when trying to make this change during the industrial production of flexible polyurethane molded foams. Maintaining cost-effective processing conditions and meeting OEMs foam characteristics, along with other issues associated with employing non-fugitive catalysts in the production of molded foams will be outlined in this paper. The Dow Chemical Company has embarked on an effort to develop the next generation of raw materials for flexible polyurethane foams. Dow recently launched a line of autocatalytic polyols, VORANOL* VORACTIV* polyols, that overcome some of the challenges associated with non-fugitive catalysts. The current VORANOL VORACTIV polyols allow the reduction of traditional fugitive amine catalysts while maintaining processing conditions and foam physical properties. This paper reports on the continued efforts by The Dow Chemical Company to produce improved VORANOL VORACTIV polyols that will allow the complete elimination of fugitive amine catalysts in the production of molded polyurethane foams. R. PRANGE The Dow Chemical Company 2301 N. Brazosport Blvd. Freeport, TX 77541 USA

INTRODUCTION Similar to auxiliary blowing agents, the role of catalysts in the production of flexible polyurethane foams is short lived. Indeed, each additive is needed during the foaming process, but they both become environmentally undesirable once the foam is made. While physical means, such as reduced atmospheric pressure, allow the elimination of blowing agents, it is quite difficult to remove catalysts from foam formulations. Several articles have been devoted to the negative effects of amine based VOC emissions and to potential alternatives to fugitive tertiary amines, todays main catalysts for HR (High Resilience) molded foams used in automotive seating [1,2,3,4]. Experience has shown that alternatives, such as non-fugitive catalysis, may have detrimental effects on foam processing, leading either to a loss of flexibility in foaming operations or to a reduction of key foam characteristics, otherwise easily achieved and maintained with conventional, fugitive catalysts. The current technical options to eliminate amine vapors are presented in Table 1. Also listed are advantages and disadvantages of each solution in terms of processing and foam aging. Analysis of Table 1 suggests that all three options have the same drawback; all have the potential to catalyze polyurethane retro-reactions. Catalysis of retro-reactions would lead to polymer degradation upon accelerated aging, making these alternatives unacceptable. However, studies carried out in Dows laboratories have shown that the negative effect of aging can be minimized by proper adjustments of the chemical composition of non-fugitive catalytic materials, especially through the use of VORANOL* VORACTIV* polyols [5].

* Trademark of The Dow Chemical Company.

TABLE 1. Options for the reduction or elimination of fugitive amine catalysts in molded foams. Solution Advantages Possible Drawbacks Possible End-results Reactive catalysts Mobility at the beginning of foaming Retro-reaction Poor foam aging Part of PU Polymer Low volatile, nonreactive catalysts Autocatalytic polyols Mobility during whole process Present in PU foam Part of PU Polymer No volatiles Retro-reaction Poor foam aging Chemical breakdown Retro-reaction Volatiles Poor foam aging

Table 2. Formulations 1-3 along with foam compression set values. Formulation 1 2 3 Polyols 100.0 38.0 38.0 VORANOL VORACTIV polyol 0 62.0 62.0 Water 4.2 4.2 4.2 DEOA 1.6 1.6 1.6 Surfactant 1.2 1.0 1.0 Fugitive catalyst package BDMAEE/TEDA(total: 0.45)a 0 0 Fugitive catalyst A 0.3 0 Fugitive catalyst B 0.3 VORANATE T-80 (index) 105 105 105 75 % CS (%) 25 48 18 75 % HACS (%) 19 38 20 a. BDMAEE: 70% bis(dimethylaminoethyl)ether in dipropylene glycol. TEDA: 33% triethylenediamine in dipropylene glycol.

BACKGROUND Two main reactions occur in parallel while polyurethane foams are produced: the water-isocyanate reaction and the polyol-isocyanate reaction. The foaming profile can either be balanced or distorted based on the level and type of catalysis used to promote these reactions. A balanced reaction profile is one that leads to the full completion of the desired reactions, i.e. reaction profiles that provide good foaming conditions ultimately produce foams with superior physical characteristics. Non-balanced reactions can lead to several side reactions during foaming, such as formation of biuret, allophanate, carbodiimide, isocyanate trimerization, etc. Most of these side reactions lead to weak polymer structures since these bonds are not stable upon heat and/or humid aging. Furthermore, these side reactions can be further detrimental by lowering the isocyanate available to complete the polymerization reactions. Consequently, a balanced catalysis is key to prevent unwanted reactions and to promote and adjust the ones that play a key role in producing a strong polymer network. For instance, S. Hashimoto demonstrated the role of neutralization of free tertiary amines by carbamic acid generated in situ to control the rate of CO2 generation [6]. Saunders and Frisch stated that high

levels of blowing catalysts tend to form amines at the expense of substituted ureas [7]. Experiences have shown that this translates to foam with poor compression set properties. In addition, urea precipitation is key for cell opening [8] and is dependent on the hydrogen bonding of the whole system, hence on its catalysis. The fact that non-fugitive amines stay within the foaming mass until the end of rise and may become part of the polymer structure makes reaction adjustments more challenging and may be detrimental to the full catalytic balance. Indeed, these amines have much less mobility than conventional, fugitive products, hence are less accessible for complexation with carbamic acid. In addition, they likely become ineffective when the viscosity of the reactants increase. In the case of reactive amines, the functionality of the compound also plays a critical role since monofunctional compounds act as chain terminators and affect the rate of gelation [9]. The effect of catalysis on compression set values, an important property of flexible foams, is demonstrated by using three different catalytic packages. Results for 75% compression sets and 75% humid aged compression sets for Formulations 1-3 are given in Table 2. As shown, the control foam (Formulation 1) was catalyzed with traditional, fugitive blowing and gelling catalysts, bis(dimethylaminoethyl)ether (BDMAEE) and triethylene-

diamine (TEDA), respectively. Formulation 2 and 3 were prepared with a VORANOL VORACTIV polyol and one of two fugitive catalysts. The control foam possess 75% compression set values that are below 30% (a typical customer specification). When employing VORANOL VORACTIV polyols, care must be taken to properly formulate the system to ensure desirable physical properties. If the system is not properly balanced (Formulation 2), physical properties will suffer. However, formulations utilizing VORANOL VORACTIV polyols can be properly designed to meet the physical properties of control foams as demonstrated by Formulation 3 which was adjusted to give a properly balanced reaction profile and desirable foam properties. This work helps to validate that foam catalysis and balanced reaction profiles are very critical in obtaining proper physical characteristics. When non-fugitive catalysts are substituted for fugitive catalysts, the situation is even more challenging, as will be explained in this paper. VORANOL VORACTIV polyols can be properly designed to overcome these challenges and meet customer requirements. Current work, as will be reported, is aimed at a 100% replacement of traditional fugitive catalysts with a VORANOL VORACTIV autocatalytic polyol while maintaining current physical properties. EXPERIMENTAL Reactivity Tests All catalytic products (fugitive catalysts, non-fugitive catalysts and autocatalytic polyols) used to make foams were tested according to a Brookfield Viscosity Test (BVT). A Brookfield rotational viscometer was used to monitor the change in viscosity of the reacting system (polyol, isocyanate and catalyst) in order to obtain an indication of the gelling activity of the catalyst. This test was conducted by blending 100 grams of polyol (for control purposes a standard polyol was used for all runs) conditioned at 25C and the desired catalyst candidate. The appropriate amount of VORANATE* T-80 toluene diisocyanate required for an index of 110 was then added, and the blend was stirred at 1,000 RPM for 30 seconds. The viscosity of the system was monitored for ten minutes or until the viscosity reached 20,000 mPa.s. The

addition of TDI to the system marked time zero for the start of the measurements. In the case of the autocatalytic polyols, no catalysts were added. Foaming Tests Machine foaming programs were performed on either a high pressure machine equipped with a Krauss-Maffei MK-12/16-4K mix-head (Meyrin) or a Cannon Model A40 high-pressure, impingement mixing foam machine (Freeport). An aluminum mold (40x40x10 cm) heated at 60C was used to prepare the foam parts. Demold time was four minutes. Molded foams were produced with six different systems as presented in Table 3. Only Formulation A, the control, was based on conventional polyol and fugitive amines. All other formulations contained VORANOL VORACTIV polyol and either conventional catalysts, autocatalytic polyols or non-fugitive catalysts as described in Table 1. Basic formulations are shown in Table 4. Free Rise Foaming Free rise foaming was performed in a 20 liter plastic bucket to measure cream, gel and rise times. Foam was cut to measure FRD (Free Rise Density) in kg/m3. Minimum Mold Fill Density Minimum mold fill density corresponds to the minimum part weight. Crushing Force at Demold Crushing force was taken as the first 50 % IFD (Indentation Force Deflection) cycle measured on foam pads one minute after demold. Hot IFD Hot IFD was taken as the first 50 % IFD cycle measured after foam crushing, 3 minutes after demold.

Table 3. Foam Formulations A-F based on various catalyst types. Formulation A B C D VORANOL VORACTIV polyol X Conventional, fugitive amine catalysts X X Autocatalytic Polyol G X Autocatalytic Polyol H X Non fugitive catalyst I Non fugitive catalyst J

E X

F X

X X

Table 4. Basic foam formulations for Formulations A-F. Formulation A B C, D SPECFLEX NC-632 70 20 SPECFLEX NC-700 30 30 30 VORANOL VORACTIV polyol 50 Triethylenediamine, 33% in dipropylene 0.40 glycol Bis(dimethylaminoethyle)ether, 70% in 0.05 dipropylene glycol Autocatalytic polyol G or H 70 Fugitive catalyst A 0.30 Non-fugitive catalyst I or J Water 3.5 3.5 3.5 Diethanol amine, 85% 0.8 0.8 0.8 Surfactant 0.6 0.6 0.6 VORANATE T-80 (Index)a 90 100 105 90 100 105 90 100 105 a. Only results obtained with index 100 will be reported hereafter.

E, F 20 30 50

Varied 3.5 0.8 06 90 100 105

Curing of Thin Sections A conventional automotive seat mold was used to assess curing of thin sections. Foam Physical Testing Foam pads were tested for physical characteristics according to the tests listed in Table 5. VOC Emission Measurements Foam samples were taken and wrapped in two layers of aluminum paper and placed in a polyethylene bag immediately after demold for shipment to the analytical laboratories. VOC emissions were measured according to VW/Audi PV 3341 and Daimler Chrysler PB-VWT709 test methods. Blend Stability Polyol blends (polyols, catalysts, water and surfactants) were foamed at different times to assess potential reactivity variations. PVC Staining Tests Accelerated aging tests at elevated temperature were carried out in closed containers in the presence of a poly(vinyl chloride) (PVC) foil. A foam sample, 50 x 50 x 50 mm was cut from the core of the molded foam pad and placed at the bottom of one-liter glass jar. A piece of gray PVC skin (reference E 6 025 373A0175A, supplied by Bennecke-Kaliko) was hung from the lid of the glass jar with a chromium-nicked alloy based string. The jar was sealed. Aging was carried out at 120C for 72

hours. After cooling, the PVC sheet discoloration was measured using a Minolta Chroma Meter CR 210. The smaller the change in color, the lower the E measured in this test. RESULTS AND DISCUSSION Foam formulations, shown in Table 4, were based on a combination of blowing and gelling catalysis. In the case of the control, the traditional amine catalyst combination of triethylenediamine (gelling catalyst) and bis(dimethylaminoethyl)ether (blowing catalyst) was used. All the other formulations were prepared with experimental autocatalytic polyols or with a VORANOL VORACTIV polyol and a co-catalyst. The gelling catalytic materials used in this work were selected by BVT test that confirmed their activation of the polyolisocyanate reaction. BVT Studies BVT curves for some gelling catalysts listed in Table 3 are reported in Figure 1. It is important to point out that BVT reactivity is mainly derived from the basicity of the catalyst and does not predict anything about its blowing efficiency once water is present. Hence these BVT data were only used to screen and compare gelling candidates, since foaming tests or reaction kinetics are needed to gather more complete information on the reactivity balance of a catalyst and/or catalyst package. Curves in Figure 1 illustrate that full gelation or rapid viscosity increase occurs after an initiation time of several minutes. This is most likely due to the use of TDI that has a sterically hindered isocyanate group in the ortho position on the toluene ring that exhibits low reactivity, hence it is slow to be activated. It is also

important to note, in regards to the BVT data, that some of the non-fugitive catalysts are reactive towards isocyanate. Thus, in some instances, the apparent catalytic activity of the non-fugitive catalyst is altered due to the reaction product between the reactive, nonfugitive catalyst and the isocyanate. Free Rise Foam Reactivity Studies

(Formulation A) with non-fugitive catalysts and autocatalytic polyols (Formulations B-F). It should be noted, however, that the end of rise time of some nonfugitive catalysts tends to be slower, most likely because of their lack of mobility.

20000

Free rise foam reactivity measurements are important to assess the behavior of the full system under unstressed conditions, i.e. when there is no shear nor any pressure applied to the foaming mass. Visual inspection of the foam rise and of its final settling, along with free rise density and cream, gel and rise times, allowed comparisons between different catalysis packages. The assessment and interpretation of these results provide a way to make any needed formulation adjustments that may be required for foaming under stressed conditions, i.e. in the mold. For instance, the data in Table 6 indicate that the level of VORANOL VORACTIV polyol in Formulations B-E (Table 4) should be reduced since the fast cream times would make it difficult to adjust other important parameters such as gel time. The data given in Table 6 also illustrate that it is possible to match the reactivity profile of conventional, fugitive, catalysts

16000 Viscosity (cPs)

12000

Fugitive Catalyst B Autocatalytic Polyol G Non Fugitive Catalyst J Autocatalytic Polyol H Non Fugitive Catalyst I

8000

4000

0 00:00 01:00 02:00 03:00 04:00 05:00 06:00 07:00 08:00 09:00 10:00 11:00 Time (mm:ss)

Figure 1. BVT curves for fugitive catalyst B, autocatalytic polyol C, non-fugitive catalyst J, autocatalytic polyol H, and non-fugitive catalyst I.

Foam Test BEFORE AGING Core Density CFD Hardness Airflow Resiliency Tensile & Elongation Tear Strength 50 % Dry Compression Set 70 % Wet CS with Skin HEAT AGING CFD Change Tensile/ Elongation Tensile/ Elongation HUMID AGING 50 % HACS 75 % HACS 50 % HACS CFD Change Tensile/ Elongation

Table 5. Foam Physical Testing. Test Method ISO 845-95 VW/AUDI PV 3410-93 ASTM D-3574-01 ASTM D-3574-01 VW/AUDI PV 3410-93 VW/AUDI PV 3410-93 VW/AUDI PV 3410-93 Renault RP 1637-81 VW/AUDI PV 3410-93 VW/AUDI PV 3410-93 Opel/GM 60.283-6-96 Opel/GM 60283-5-96 Opel/GM 60283-5-96 VW/AUDI PV 3410-93 VW/AUDI PV 3410-93 VW/AUDI PV 3410-93

Conditions (units)

40 % deflection (KPa) Cfm (cubic foot/minute) (%) 30 mm thickness (KPa) 10 mm thickness (N/m) 50 % CT (%) 70% CD with skin (%) 40% deflection (%) 200 hours at 90C 22 hours at 140C 5 hours 120C, 100 % RH (% Cd) 5 hours 120C, 100 % RH (% Cd) 200 hours at 90C (% CT) 40 % deflection (%) 30 mm thickness (Kpa)

Table 6. Free rise reactivity (index 100).

Formulation Cream time (s) Gel time (s) Rise time (s) Free rise density (kg/m3)

A 6 60 118 29

B 4 50 90 27

C 3 50 100 28

D 4 70 141 28.5

E 4 62 116 27.5

F 5 59 130 30.5

Formulation Minimum molded density (kg/m3) Mold exit time (sec) Part weight (g) Molded density (kg/m3) Curing thin section Crushing Force (N) Hot IFD (N)

Table 7. Processing study of molded foam (index 100). A B C D 32 32 36 37.5 37 29 25 39 610 592 595 600 38.7 37.5 37.5 37.5 Limit Limit Limit No 1,280 1,030 730 220 195 170 120 130

E 36 34 608 38 Limit 690 200

F 35 40 606 38 Limit 1,020 160

Formulation 40 % IFD (N) Core Density (kg/m3) 40 % CFD (Kpa) Airflow (cfm) Resiliency (%) Tensile Strength (Kpa) Elongation (%) Tear Strength (N/m) Cell structure

Table 8. Molded foams physical properties before aging. A B C D 195 200 225 251 36.7 36.0 37.2 38.5 3.4 3.4 3.5 4.5 3.4 3.4 2.6 4.5 64 64 65 64 107 150 112 121 118 140 111 120 204 200 218 294 Normal Normal Normal Normal

E 247 36.7 4.6 3.4 57 138 148 322 Normal

F 208 35.6 3.6 3.4 64 81 99 146 Normal

Processing Studies of Molded Foam Five parameters were recorded to assess processing conditions of Formulations A-F. As outlined in Table 7: minimum molded density indicates how well the system flows inside the mold and the stability of the foaming mass; mold exit time is indicative of the reactivity during the first phase of foam rise; curing of thin section is a key parameter when producing a wide range of automotive parts; crushing force is related to the level of closed cells inside the foam at demold; and hot IFD is a measure of foam cure inside the thicker part of the molded pad. The data in Table 7 call for several comments. First, it is clear that formulations A and B based on conventional, fugitive catalysis allows reaching the lowest molded density while still maintaining an acceptable crushing force. Formulation D gives very open foam, but possesses a slow cure rate as shown by the low value of hot IFD. Curing of thin section, even with the control formulation is still critical for all foams with a fourminute demold time. Finally, comparison of the control

and the experimental formulations indicates that formulations with non-fugitive catalysis packages perform poorly overall in the foaming process. This is not unexpected, based on what has been discussed in the background section. Physical Properties Before Aging of Molded Foam The main properties before aging of these six foams are reported in Table 8. The effects of catalysis changes show differences between these foams, even with comparable cell structures and air breathabilities. This trend is consistent with the foams of Table 2, as the same polyol systems, crosslinkers, water levels and surfactants were used in the formulations. The most striking variations between formulations A-F are related to foam hardness and core density. Knowing that all the parts have approximately the same molded densities, the data suggest that the various formulations have different skin densities.

Table 9. Dry and humid aged compression set and wet skin properties molded foam after humid aging. Formulation A B C D E

50 CS (%Cd) 50 % HACS 75 % HACS 70 % Wet CS with skin

5.3 20 18.4 31.1

5.2 18.7 21.7 32.8

4.8 18.3 15.8 22.5

6.2 18.2 16.6 22.6

5.7 19.6 17.5 31

6.5 32 37 27.8

Table 10. Physical properties of molded foams after VW humid aging. Formulation A B C D E VW 40% CFD change + 45 + 35 + 12 -1 Degraded Tensile (Kpa) 96 122 126 85 Degraded % Change Tensile - 10 - 23 + 10 - 30 Degraded Elongation (%) 155 191 159 138 Degraded % Change Elongation + 31 + 36 + 43 + 15 Degraded Degraded: Foams with tensile strength below 50 Kpa and/or less than 60% elongation.

F Degraded Degraded Degraded Degraded Degraded

Molded Foams: Dry and Humid Compression Sets Data in Table 9 demonstrate that systems with properly balanced reactions have good compression set values after dry and humid aging. Formulation F, based on catalyst J, is a good example of the negative effects that a distorted catalysis system can have on physical properties. Figure 2 illustrates that while Formulations A-E meet typical customer specifications for humid aged sets, Formulation F falls short of passing humid aging test specifications typically set by European and North American OEMs. Molded Foams: Physical Properties after Humid and Heat Aging While Formulations A-E possess good compression set values after humid aging, their physical integrity has been damaged during this process. The data given in Table 10 show the effect that humid aging can have on foams prepared from non-traditional catalysts packages and provides further evidence to properly balance the catalysis. As shown, Formulations E and F, prepared with a combination of a VORANOL VORACTIV polyol and a non-fugitive co-catalyst, produce foams that degrade during VW humid aging. Furthermore, Formulation E based on catalyst I is weakened by heat aging, as demonstrated by the tensile strength and elongation shown in Table 11. The distorted catalysis of these formulations promoted multiple side reactions during foaming that resulted in a weak polyurethane

network that degrades with aging upon the occurrence of retro-reactions. We share these data to illustrate the importance of properly balancing the catalysis and the negative impact an unbalanced reaction profile can have on physical properties. Dow is continuing to work on developing a range of autocatalytic polyols that will produce balanced polyurethane reaction profiles that are capable of producing foams with desirable foam physical properties. Formulations C and D, prepared from experimental autocatalytic polyols G and H respectively, are good examples of the work that we are doing in this area. These polyols produce foams that have similar properties as the control, as demonstrated by the data given in Tables 9-11.

40 35 30 % HACS 25 20 15 10 5 0 A B C Formulation D E F 50 % HACS 75 % HACS Typical Spec for Humid Aged Set

Figure 2. Compression set properties after humid aging.

Table 11. Physical properties of foams after heat aging. A B C D VW 40% CFD change 2 -2 -5 -9 Tensile (Kpa) 129 167 132 139 Tensile % Change 21 11 18 15 Elongation (%) 139 185 125 130 Elongation % Change 18 32 13 8 22 Hr, Tensile (Kpa) 173 175 111 160 140C Tensile % Change 61 23 0 32 Elongation (%) 184 228 229 215 Elongation % Change 56 63 106 79 d. Degraded foam: Foams with tensile strength lower than 50 Kpa and/or elongation less than 60%. Formulation 200 Hr, 90C

E -19 145 5 198 34 d d

F -5 113 40 128 29 130 60 205 107

Volatile Organic Compound (VOC) Emissions VOC emissions associated with amine catalysts can be eliminated when VORANOL VORACTIV polyols are employed in the production of molded foams. Four methods were utilized to obtain VOC emissions on Formulations A-C. As reported in Table 12, the autocatalytic polyol approach utilized by Dow (Formulation B and C) significantly lowers the VOC emissions, regardless of how measured, when compared to the control foam (Formulation A) prepared with a traditional, fugitive catalyst package. The decrease in VOC emissions with the use of autocatalytic polyols is illustrated in Figure 3. As shown, VOC emissions decrease when going from traditional fugitive amine catalysts to PU molded foams prepared with a VORANOL VORACTIV polyol. Further evidence for the reduction of total VOC emissions can be seen by examining the chromatograms (Figures 4-7) obtained on Formulation A and B according to the PB-VWT-709 method for VOC and FOG. As shown, no VOC

emissions relating to catalytic amines were detected as a component of the foam produced from Formulation C, which utilized experimental autocatalytic polyol G.

900 800 700 600 g x/ g 500 400 300 200 100 0 A B C VOC as Toluene (PB-VWT-709, x=toluene) FOG (PB-WT=709, x=hexadecane) Carbon emission (Audi PV 3341, x=C)

10 9 8 7 6 5 4 3 2

Figure 3. VOC emissions for Formulations A-C.

Table 12. VOC Emissions obtained from foam produced with Formulation A, B and C. Carbon emission VOC as Toluene VOC (HS/GC/MS) FOG (Audi PV 3341) PB-VWT-709 PB-WT=709 (g perdeuterotoluene /g) (g toluene/g) (g hexadecane/g) (g C/g) Reference foam A B C 9.9 6.2 5.1 847 728 545 143.7 31.7 35 684 643 200

100

80

Silicon containing components

CH3 N H3C N

*
O

NH

100

C4H9

* * *

80
H3C N

CH3

* *

* *

Silicon containing components

60

60

NH

O N

C8H 17

40

H3C

N CH3

40
H3C N CH3

20

20

*
0 250 500 750 1000 1250

500

1000

1500

Figure 4. VOC chromatogram of Formulation A.

Figure 6. FOG chromatogram of Formulation A.

100

80

Silicon containing components

** * **

100

Silicon containing components

NH

80

C 4H9

* **
NH

60

60

C8H17

40

40

20

20

0 500 1000 1500

0 250 500 750 1000 1250

Figure 5. VOC chromatogram of Formulation C.

Figure 7. FOG chromatogram of Formulation C.

PVC Staining Study Amine VOC emissions are believed to contribute to PVC staining. PVC staining data were obtained on foams produced from Formulations A, B and D. As shown in Figure 8, a change in the PVC color occurs in all instances. Formulation A, produced with fugitive catalysts, promoted the highest degree of PVC staining. Formulation B, prepared with a VORANOL VORACTIV polyol and a reduced amount of fugitive catalyst, shows less PVC staining than Formulation A. Formulations D, based on experimental autocatalytic polyol H, showed the lowest level of PVC staining.

CONCLUSION The current work confirms the good performance of VORANOL VORACTIV polyols as a partial substitute for fugitive amine catalysts in automotive flexible molded foams. This work also illustrates that many challenges have to be addressed when looking for complete elimination of fugitive amine catalysts and replacement with non-fugitive systems. Progress has been made and continues to be made. Learnings from this and other work have led to new product developments within our laboratories. This will be the subject of a future report. ACKNOWLEDGEMENTS

25 20 15 Absolute value 10 5 0 -5

Delta b Yellow Delta a Red Delta E Delta L Black Delta b Blue

-10 -15 -20 A B D PVC control

The authors wish to thank their many Dow colleagues who had a role in generating data presented in this paper and whose helpful discussions have led to the continued development of this work. Special thanks are extended to Jim Cosman, Jean Courtial, Hugo de la Ruelle, Ray Drumright, Chris Noakes, Philippe Osch, Ross Polk, Alan Schrock, and the Meyrin and Freeport testing laboratories.

Figure 8. PVC staining results.

REFERENCES 1. Mercando, L.A., J.G. Kniss, J.D. Tobias, A. Plana, M.L. Listermann, and S. Wendel. 1999. Non Fugitive Catalysts for Flexible Polyurethane Foams, Proceedings of the Polyurethanes EXPO 99, Technomic: Lancaster, PA., 103-134. Sikorski, M., C. Wehman, and H. Cordelair H. 1999. New Additive Solutions for Low VOC in HR Molded Foams, Proceedings of the EXPO99 Technomic: Lancaster, PA., 135-144. Masuda, T., H. Nakamura, Y. Tamano, H. Yoshimura, R. Van Maris, and K.M. Gay. 2002. Advance in Amine Emission Free Catalyst Systems for Automotive Seatings A Fundamental Study on Durability Performance by Humid Aging Load Loss Test (HALL), Proceedings of the Polyurethane Conference 2002, Technomic: Lancaster, PA 189198. El Ghobary, H., L. Muller, E.J. Derderian, and K.K. Robinson. 2003. New Low Fogging, Low Emissions Urethane Additives for Automotive Moulded Foam Proceedings of the UTECH 2003 Conference, Crain Comunications, London. Sonney, J.M., F.M. Casati, A. Fanget, and J. Godoy. 2003 Development of Low-VOC Polyurethane Foam Formulations for the Automotive Market Based on Catalytically Active Polyols Proceedings of the UTECH 2003 Conference, Crain Communications, London. Hashimoto, S. 1981. Catalysts for Polyurethanes and Polyisocyanurates International Progress in Urethanes, Vol. 3, Technomic, Westport, CT, 43-82 Saunders, J.H. and K.C. Frisch. 1962 Polyurethanes: Chemistry and Technology, Part I, High Polymers Vol. XVI, Interscience Publishers, pp 77 and 334. Park, H.H., J.B. Park and H. Ueda. 2002. Non Crushing Foams systems for Automotive Seat, Proceedings of the Polyurethane Conference 2002, Technomic: Lancaster, PA., 61-69. Rodriguez A. Polyols Compatible with Nonfugitive amine catalysts, Proceedings of the UTECH 2003 Conference, Crain Communications, London.

BIOGRAPHIES Franois M. Casati Franois M. Casati graduated from ICPI (F), now CPE-Lyon (Ecole Superieure de Chimie Physique Electronique de Lyon), in 1967. He has over 30 years of experience in Polyurethanes, Industrial Amines and Biocides, with S.N.P.E., Recticel, Abbott Laboratories, BP Chemicals and The Dow Chemical Company. During that time he has held various positions in Manufacturing, Marketing and Research & Development. He is currently working as a Product Development Leader for the Flexible Foam business of Dow. Alain Fanget Alain Fanget joined the Geneva-based Polyurethane Research and Development group of Union Carbide Europe in 1978 and was then transferred to BP Chemicals in 1979 and to The Dow Chemical Company in 1989 where he worked in various PU molding and ACES applications. He is currently a senior Technical Service Specialist in the Automotive Thermosets R&D Group of the Meyrin International Development Center, with specific responsibilities in seating and NVH molding applications. Jose Godoy Dr. Jose Godoy graduated from the University of Geneva (Switzerland) and received his Ph.D. in Organic Chemistry from the same University in 1983. After a post-doctoral research fellowship at Imperial College of Science and Technology in London on the synthesis of natural products, back to Geneva, he worked for a World Health Organization program on synthetic molecules against Malaria. From 1987 to 1989, he worked in the Geneva-based Research and Development group of BP Chemicals and was transferred to the Dow Chemical

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Company in 1989. He is currently a Senior Specialist in the Flexible Molded group in Meyrin. Robbyn Prange Robbyn Prange has a B.S. chemistry degree from Hope College and a Ph.D. in polymer chemistry from The Pennsylvania State University. She joined The Dow Chemical Company in 2001 and has experience working with thermoset systems and dispersions. Robbyn is currently a Senior Research Chemist in the Polyurethanes Flexible Foam Group. Jean-Marie Sonney Dr Jean-Marie Sonney graduated from the Swiss Federal Institute of Technology in Lausanne (Switzerland) and received his Ph.D. degree in physical organic chemistry from the same institution in 1979. After a post-doctoral research fellowship at the University of California, Santa Cruz, he joined the Geneva-based Research and Development group of BP Chemicals in 1981 and was transferred to the Dow Chemical Company in 1989. During this period, he had various responsibilities in the field of Analytical Chemistry, Quality Assurance, EH&S, Quality Management and Technical Service. He is currently a Senior Development Specialist in the Development Group for Flexible Foams. *Trademark of The Dow Chemical Company.

For Additional Information:

The Dow Chemical Company Customer Information Group P.O. Box 1206 Midland, MI 48641-1206 Telephone (800) 441-4369 Website: www.dow.com

*Trademark of The Dow Chemical Company

Form No. 109-01666-903QRP