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Elimination of Amine Emissions from Polyurethane Foams: Challenges and Opportunities F.M. Casati, J.M. Sonney, H.

Elimination of Amine Emissions from Polyurethane Foams:

Challenges and Opportunities

from Polyurethane Foams: Challenges and Opportunities F.M. Casati, J.M. Sonney, H. Mispreuve, A. Fanget, R.
from Polyurethane Foams: Challenges and Opportunities F.M. Casati, J.M. Sonney, H. Mispreuve, A. Fanget, R.

F.M. Casati, J.M. Sonney, H. Mispreuve, A. Fanget, R. Herrington, J. Tu

Reprinted from The API 2001 Proceedings with permission from the Alliance for the Polyurethanes Industry.

Elimination of amine emissions from polyurethane foams:

challenges and opportunities

F.M.F.M.F.M.F.M. CASATI,CASATI,CASATI,CASATI, J.M.J.M.J.M.J.M. SONNEY,SONNEY,SONNEY,SONNEY, H.H.H.H. MISPREUVE,MISPREUVE,MISPREUVE,MISPREUVE, A.A.A.A. FANGETFANGETFANGETFANGET Dow Europe S.A International Development Center 13, rue de Veyrot - P.O. 3 CH-1217 Meyrin 2 (GE) Switzerland

ABSTRACT

Polyurethanes are a unique class of plastic in the sense that independent manufacturers buy liquid polyols and isocya- nates and then react them in the presence of catalysts, sur- factants and other additives in widely varying processing schemes to make the final commercial product. In some manufacturing scenarios, there is a growing concern about worker exposure to volatile organic chemicals (VOC) such as the amine catalysts. Emissions from manufactured arti- cles that contain polyurethane components are also a con- cern.

The polyurethane industry is continuing its legacy of suc- cessfully reducing the amount of volatile organic chemicals released from its operations. Examples of this include the total elimination of the classical chlorofluorocarbon blow- ing agent from flexible foams and the replacement of vola- tile antioxidants with less migratory ones. Today, many of the classes of ingredients commonly used in preparing polyurethanes are available in low-fogging or low VOC grades. The next big challenge being addressed by the in- dustry is the elimination of amine catalyst vapors. This is important for both VOC and odor concerns.

The catalyst suppliers have responded by introducing a variety of new, non-fugitive (sometimes called reactive) amine catalyst compositions. Their success at reducing amine emissions while providing catalytic activity is widely reported in the literature. Difficulties associated with reac- tivity profile adjustment, higher usage levels and losses in certain foam physical properties suggest that an improved level of technology is still needed. This paper will present a review of work The Dow Chemical Company is doing to develop flexible foam grades of polyether

R.R.R.R. HERRINGTON,HERRINGTON,HERRINGTON,HERRINGTON, J.J.J.J. TUTUTUTU The Dow Chemical Company 2301 North Brazosport Freeport TX 77541 U.S.A.

polyol that help reduce and in some cases eliminate cata- lysts while improving process. Comparative data will be presented to illustrate the utility of these new polyols in helping the polyurethane industry continue to reduce vola- tile emissions.

INTRODUCTION

Flexible polyurethane foams are well-established industrial products with important technical and economic advan- tages. These materials have found their way into our daily lives through their use in the endless array of consumer products. To complement this wide-ranging success, sig- nificant development efforts continue today to improve targeted performance features like comfort, durability, re- sistance to moisture and temperature [1-3]. Improvements in the environmental impact of these products are also be- ing gained through reductions in the amount of VOC’s re- leased during their manufacture. In some manufacturing scenarios, there is a concern about worker exposure to the vapors of traditional amine catalysts. Amine emissions from manufactured articles containing polyurethane com- ponents is a growing debate due to potential fogging, PVC (PolyVinyl Chloride) staining and PC (Poly Carbonate) degradation [4-6].

The industrial hygiene and safety issues related to handling and use of amine catalysts in polyurethane production are complex. It begins with the need to purchase one or more of these additives in separate containers that must be off- loaded, warehoused, transported to the formulation room and in many cases physically handled by workers assigned the task of blending up a formulation. Most amine catalysts have exposure and odor properties such that personal pro- tective equipment is required [7]. Empty working and shipment vessels need to be properly handled and prepared for disposal or shipment back to the vendor.

Due to the exothermic nature of the reactions and the extra heat applied in some curing scenarios, freshly prepared polyurethane products are always at an elevated tempera- ture. With the classical non-reactive type amines, odorous vapors are released and in the absence of proper ventila- tion, worker exposure can occur [8-10]. When captured by an exhaust system, these amine vapors can represent a sig- nificant contribution to the total VOC’s being released by the manufacturing plant.

Even after cooling down and undergoing fabrication into finished products, trace amine odors are sometimes still detectable. Amine catalyst vapors have been identified as one component of the new car smell [11].

The catalyst suppliers have responded by introducing a variety of new, non-fugitive (sometimes called reactive) amine catalyst compositions. Examples of their success at reducing emissions while providing catalytic activity are recorded in the literature [12-18]. Difficulties associated with reactivity profile adjustment, higher usage levels and losses in certain foam physical properties suggest that an improved level of technology is needed.

In this paper, we continue to report the previously an- nounced activities at Dow to develop active polyether polyols [19]. Comparative data will be presented to illus- trate the utility of these new polyols in helping the polyu- rethane industry continue to reduce volatile emissions.

BACKGROUND

Most commercially manufactured polyurethane foams are made with the aid of at least one catalyst. Many classes of compounds have been investigated and the amines and the organo-metallics have been found most useful. Various combinations of catalysts are used in order to establish a balance between the chain propagation or gelling (isocya- nate with polyol) reaction and the blowing reaction (iso- cyanate with water). Any given catalyst molecule will normally have some activity for both reactions and it is common to find synergistic performance when using two or more catalysts in a formulation. The polymer formation rate and the gas evolution rate must be balanced so that the gas is entrapped efficiently in the gelling polymer while the foam cells develop sufficient strength to maintain their structure without collapse or shrinkage. Catalysts are also important for assuring completeness of reaction or “cure” in the finished foam. Some of the challenges to success in designing a catalyst package for a polyurethane production reaction are listed in Table 1.

Table 1. Challenges to catalyze polyurethane reactions

Solubility parameters (including water)

Steric hindrance

Difference of NCO reactivity between isomers

Acidity

Viscosity build-up

Effect of temperature on catalyst efficiency

The first requirement for good catalytic activity is that the catalyst molecule be highly compatible with the mixture of reaction raw materials. Molecular structure of the catalyst and the resulting steric hindrance will impact how easily the molecule can approach the reactants and facilitate the desired reactions [20]. The catalyst package needs to be effective when isocyanates of varying isomer content and reactivity are used. Trace acidity, common in some raw materials, impact the performance of the catalyst(s). Mo- lecular mobility of the catalyst should be high so that it can continue to exert its effect as the system reacts and builds viscosity. Since the reactions are exothermic, the catalytic effect should not be overly influenced by a rise in tem- perature.

All of these requirements are more easily met with the con- ventional, fugitive type amines rather than the newer reac- tive type amines. To address these challenges, the reactive amines are normally used at significant higher concentra- tions, hence sometimes are not fully bound in the polymer network [21]. In addition, most of the reactive amines are mono-functional and can be considered as polymer chain terminators (which generally detracts from the ultimate properties of the polymer). Dow active polyols are useful to overcome these challenges.

EXPERIMENTAL

A list of all raw materials used with this study is given in Tables 2, 3 and 4 (SPECFLEX *, VORANOL *, VORANATE *, ISONATE * are trademarks of The Dow Chemical Company).

Table 2. List of raw materials

SPECFLEX NC 630

Polyether polyol

SPECFLEX NC 632

 

VORANOL CP 6001

 

VORANOL CP 1421

 

VORANOL 3137 A

 

SPECFLEX NC 700

SAN

copolymer polyol

SPECFLEX NE 150

MDI

isocyanate

VORANATE T-80

TDI

isocyanate

Table 3. List of catalysts

Trademark

Supplier

DABCO NE-200

Air Products

DABCO NE-1060

DABCO 33 LV

DABCO BLV

DABCO VP 137

DABCO T

TOYOCAT RX-20

Tosoh

TOYOCAT RX-21

PC-CAT HPI

Nitroil

DMAMP-80

Angus

NIAX A-1

Crompton

JEFFCAT ZF-10

Huntsman

(DABCO* is a trademark of Air Products & Chemicals Inc; TOYOCAT * is a trademark of Tosoh Corporation; NIAX * is a trademark of Crompton Corporation; JEFFCAT * is a trademark of The Hunstman Corporation; PC-Cat * is a trademark of Nitroil Europe Handels GMBH; DMAMP-80* is a trademark of Angus Chemical Company)

Table 4. List of Dow Experimental Active Polyols

 

OH number

Functionality

EO capping

Polyol A

56

3

no

Additive A

56

<2

yes

Polyol B

32

>3

yes

Polyol C

32

>3

yes

Foam Preparation

Foam formulations are indicated with each section of the paper. Bench scale molded foams were produced in a 30x30x10 cm test block mold heated at 60°C using the standard hand-mix procedure [22]. Free-rise foams were poured in a card-board box.

Slabstock foams were either produced on a POLYMECH or on a VARIMAX machines. For MDI HR molding high pressure impingement mixing machines (KRAUSS- MAFFEI and CANNON) were used to pour foams in a 40x40x10 cm standard test block mold and in a variety of production seat molds.

Foams for the processability studies in low-density TDI- based HR molded foams were prepared in a Hi-Tech Engi- neering Model RCM-40 high pressure, impingement mix- ing foam machine. The machine was retrofitted with an Admiral brand, L-type (10/14) mixing head. Two process streams (isocyanate and polyol masterbatch) were used. Nominal throughput of the machine was 10 kg/min (22 pounds/minute) at the component ratios necessary to maintain a 105 isocyanate index for all foams made during this study.

Molded Foam Processing Tests

The protocol for testing foam processability factors have

been described in detail [22] and will be further discussed

below. A variety of heated aluminum molds of various

shapes were used to evaluate the processing characteristics

of both control and experimental foam formulations.

Foam Testing

Foam physical properties were determined in accordance with ASTM, ISO, NF and major OEM’s (Original Equip- ment Manufacturers) testing procedures.

PVC Staining Tests

Accelerated aging tests at elevated temperature were car- ried out in closed containers in the presence of a PVC foil. A foam sample of 50x 50 x 25 mm was cut from the core of the foam part which had been isolated just after production and was placed at the bottom of a 1 liter glass jar. A piece

of gray PVC skin, reference E 025 373A0175A, supplied by Bennecke-Kaliko (Germany), was hung by the rim of the jar, which was then sealed. Aging was carried out at 115°C for 72 hours. After cooling, the PVC sheet discol- oration 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

Dow newly developed active polyols were tested in various conditions with different technologies. The purpose of this work was to assess their performance and to define how they can be formulated to reduce and in some cases elimi- nate amine catalyst use. Initial work had been concentrated on the performance of reactive amines offered by the vari- ous suppliers and on their combination with Dow’s active polyols. In most cases it was found that these products gave good compatibility with Dow active polyols and that, by allowing a reduction of their concentration in polyurethane formulations, overall processing was improved.

Main results of this study are presented hereafter with vari- ous technical options. These are concentrated on flexible foams since these are the focus of this research program. Each foam technology will be reviewed and discussed separately.

SLABSTOCK FOAM

Dow’s experience with slabstock foam has shown that most common density range can be produced without the addi- tion of traditional amine catalyst. Experimental Polyol A can be used alone to provide a smooth rise profile for low density (16kg/m³) formulations using all-water blowing. Rise rate of such formulation is identical to that of tradi- tional amine catalyst blown formulations (Figure 1). Addi-

Rise Rate

Rise Rate

tive A was used, together with Polyol A in formulations, especially those with low water level, where more blowing is necessary. Figure 2 illustrates rise rate comparison of 3.7 PHP (parts per hundred parts of polyol) water formulations with the new active Polyol A. With tuning of additive A, a rise rate similar to that of traditional amine catalyst can be reached.

6.5 Water Formulation

14 12 10 8 0.12Dabco BLV Exp. Polyol A 6 4 2 0 0 20
14
12
10
8
0.12Dabco BLV
Exp. Polyol A
6
4
2
0
0
20
40
60
80
100
120
140

Second

Figure 1. Rise profile of 6.5 water formulation

Rise Rate , 3.7 Water Formulation

14 12 10 8 6 4 2 0 0 20 40 60 80 100 120
14
12
10
8
6
4
2
0
0
20
40
60
80
100
120
140

Second

Dabco BLV 0.15 pphp Exp. Polyol A + Add. A 0.7 pphp

Figure 2. Rise profile of 3.7 water formulation

Foams made with these new experimental polyols have identical physical properties with that of traditional amine blown foams, as can be seen in Table 5.

Table 5.

physical properties

Slabstock foam: Formulation and foam

Foam formulations

 

ABCD

   

TDI INDEX

115

115

110

110

VORANOL 3137A

100

100

Exp.POLYOL A

100

99.3

Exp ADDITIVE A

0.7

WATER

6.5

6.5

3.7

3.7

DABCO DC-5160

1.2

1.2

1

1

DABCO BLV

0.12

0.15

DABCO T-9

0.15

0.15

0.21

0.21

Reactivity

       

Cream Time (sec)

13

13

12

12

Rise Time (sec)

90

91

101

103

Foam physical properties

       

CORE DENSITY (kg/m 3 )

16.8

17.6

26.9

26.6

90% COMPRESSION SETS CD (%)

9.7

11.2

2.4

2.8

TEAR STRENGTH (N/m)

227

227

315

315

ELONGATION @ BREAK (%)

68

66

107

109

TENSILE STRENTH (Kpa)

85

91

90

92

IFD HARDNESS (N) Mean Load at 25% Deflection

201

211

203

193

Mean Load at 65% Deflection

381

399

366

354

Mean Load at 25% Return

110

114

141

135

Mean Modulus

1.89

1.89

1.80

1.83

RESILIENCY (%)

21

32

41

42

Foams made with experimental Polyol A were tested for PVC staining after production in order to detect any amine emission. No staining was observed. In conclusion, it is feasible to consider that a slabstock foamer may in the fu- ture produce foam by just mixing polyols, water, surfactant and isocyanate.

MDI HR MOLDING

An emphasis has recently been put on elimination of amine emission in MDI based HR molding while maintaining good humid aging resistance. Severe tests, such as BMW’s, VW-Audi’s, Volvo’s, Opel-GM’s are already challenging when using conventional catalysis, as it has been described in previous articles [1,23]. The situation becomes more difficult when using reactive amine catalysts for the fol- lowing reasons:

1) The catalyst level has to be increased in the formulation to maintain equivalent reactivity. Since these reactive catalysts are tied up in the polymer, they tend to disrupt it somewhat. 2) The gellation profile is changed when strong, fugitive catalysts such as TEDA (Triethylenediamine) are replaced with reactive amines. Hence the polymer build-up is slowed down or at least made differently. 3) With the high concentration of tertiary amines in the polymer chain there is always a possibility of retro- reaction, or chemical degradation, upon foam exposure to a combination of heat and moisture. Indeed polymer mor-

phology changes induced by accelerated aging are already reported with conventional foam systems [24].

The present work was focused onto the use of Active Polyol B together with reduced amount of conventional amines and/or reactive amines in order to meet VW-AUDI ’s technical (T2524-03) and environmental (PVC staining) requirements. This program is still underway at the time of writing this paper. Initial results presented in Table 6 con- firm that HACS’s (Humid Aged Compression Set) values of < 15 % are easily met and PVC staining is minimized. More challenging is the HALL (Humid Aged Load Loss), or CFD (Compression Force Deflection) change at 40 % deflection after humid aging, specifications of (-25 < HALL % < + 10) when fugitive amines are removed. Foam density of the tested foams was purposely reduced vs the 52 kg/m 3 target to assess the limits.

Table 6. MDI HR molding

Formulation

A

ABB

C

C

VORANOL CP 6001

64

64

49

49

64

64

SPECFLEX NC632

 

34

34

   

34

34

VORANOL CP 1421

2

2

2

2

2

2

Exp. Polyol B

     

49

49

   

Water

 

3.7

3.7

3.7

3.7

3.7

3.7

Niax A-1

 

0.12

0.12

0.06

0.06

   

Dabco 33-LV

 

0.35

0.35

0.27

0.27

   

Catalyst A

         

0.20

0.20

Catalyst B

         

0.50

0.50

Diethanolamine LF

 

0.60

0.60

0.60

0.60

0.60

0.60

Tegostab B-8715 LF

0.50

0.50

0.50

0.50

0.50

0.50

SPECFLEX NE-150

           

Index

 

85

105

85

105

85

105

Reactivity

             

Gel time (s)

 

52

57

60

66

74

78

Properties

             

Molded

density

45.3

45.0

45.0

45.2

45.1

45.6

kg/m 3

 

40

% CFD (Kpa)

3.3

6.6

3.8

7.8

3.7

6.8

Airflow (cfm)

 

1.2

0.9

2.3

1.8

2.4

1.8

50

% CS (%) (CT)

3.2

4.6

5.4

8.0

6.4

7.4

Humid aging

             

50

% HACS (%)

7.5

11.9

7.5

10.7

8.9

9.5

CFD

change

4 th

18.4

20.7

23.7

26

24.5

30.1

cycle (%)

PVC staining

             

E

 

5.5

1.2

0.3

2.9

0.3

0.7

TEGOSTAB* is a trademark of Goldschmidt A. G.

All foam physical properties were measured according to VW’s PV 3410 test methods. Catalyst A is N,N,N’- Trimethyl N’-Hydroxyethyl-bis-Amino Ethyl Ether and Catalyst B is 2-Hydroxypropyl Imidazole.

Dual-Hardness molded parts have been produced with ac- tive polyols and based on formulations similar to the one given in Table 6 without any difficulties. Square pads were also made with 100 parts of Polyol B and no catalysts with demolding times between 4 and 5 minutes, depending on the isocyanate index. Foam properties were found similar to the ones shown in Table 6 with Formulation C.

T-80 HR MOLDING

For introduction to the TDI-based HR molded foam mar- ket, we targeted Active Polyol C that would allow foam producers to lower their added catalysts levels by 50%. We reasoned that this would significantly reduce worker expo- sure and lead to foam processes and products with much less volatile emissions.

Improvement, or at least equivalence, in both foam proc- essing and physical properties is important for the commer- cial success of any new product. Data demonstrating the performance of a molded foam grade of active polyol in these areas will be presented using the formulations given in Table 7. Note that for comparison purposes, we included a formulation based on the control polyols but at 50% re- duced catalysts. At nominal packing levels, this formula- tion typically gives molded foams at a core density of 32 kg/m 3 (2.0 lb/ft 3 ).

Table 7. Formulations for low-density TDI HR molded

foams.

 

Control

Control

Active

Component

At Full

At 50%

Polyol C

Catalysts

Catalysts

At 50%

Catalysts

SPECFLEX NC 630

62.5

62.5

 

Exp. Polyol C

   

62.5

SPECFLEX NC 700

37.5

37.5

37.5

Niax Y-10184

1.2

1.2

1.2

Diethanol Amine, pure

1.6

1.6

1.6

Dabco 33-LV

0.35

0.17

0.17

Niax A-1

0.08

0.04

0.04

Water

4.2

4.2

4.2

VORANATE T-80 Index

105

105

105

Masterbatch Viscosity,

3450

3700

3600

mPa s at 25°C

Also listed in Table 7 is the resultant masterbatch viscosity for each formulation. The masterbatch is that premixture of

ingredients that will be combined with isocyanate in the mixing head in order to cause a foam producing reaction to begin. High viscosity here makes it difficult for the foam machine to accurately meter, mix and dispense the foam producing chemicals. A practical limit for many commer- cial foam machines is taken as 5000 mPa s. The formula- tion based on the new Active Polyol C is comparable to the two control formulations and well below the stated limit.

Foam Processing

The ability to benchmark important factors related to how well a foam formulation will process on foam making equipment is helpful in the development and commercial introduction of new products. With Dow’s in-house facili- ties and testing capabilities, candidate products undergo rigorous testing for the following list of processability fac- tors.

Table 8. HR foam processability factors

Masterbatch Viscosity

Free-Rise Bulk Stability

In-Mold Flowability

Vent Stability

Rise Profile

Shrinkage

Force-to-Crush

Cure

Foam Stability

The production of defect-free molded foam parts requires that the candidate foam system possess an adequate level of stability through each stage of the foam reaction. The dif- ficulty of maintaining adequate stability has increased as foam density has decreased and part designs have gotten thinner and more complex in shape.

Free-Rise Bucket Foams

An easy way to measure overall stability of the bulk foam is the free-rise bucket test illustrated in Figure 3.

foam is the free-rise bucket test illustrated in Figure 3. Figure 3. Free-rise bucket test for

Figure 3. Free-rise bucket test for bulk stability.

In this test, a 22.7-liter (five imperial gallons) plastic bucket receives a shot from the foam-dispensing machine. The shot size is sufficient to totally fill the bucket with an approximate 10-centimeter (3.9-inch) crown of foam above the top of the bucket. Typical data recorded would include time to reach the top of the bucket, maximum and final foam height and an internal foam stability rating.

The internal stability rating is obtained by cutting the cured foam in half (parallel to the direction of rise) and ranking the severity of voids on a 1 to 10 scale. A perfect foam would receive a 10 rating while a collapsed foam would be rated at 1. This grading is easily done by visual comparison of the candidate foam to a series of similar foams with pre-

viously established ratings. The data in Figure 4 show that all three foam formulations from Table 7 perform excellent in this test.

Free Rise Stability, Blair Units Typical 9.5 9.5 9.5 10 9 Pass 8 Fail 7
Free Rise Stability, Blair Units
Typical
9.5
9.5
9.5
10
9
Pass
8
Fail
7
6
5
4
3
2
1
0
Control
Control
Polyol C
At Full
At 50%
At 50%
Catalysts
Catalysts
Catalysts

Figure 4. Comparative free-rise stability performance.

Figure 4. Comparative free-rise stability performance. Figure 5. In-mold flowability test. In this test, the

Figure 5. In-mold flowability test.

In this test, the mixture is dispensed into one end of a 38.1 x 76.2 x 6.3 cm (15 x 15 x 2.4 in) heated mold and pur- posely forced to flow over three rounded humps on its way to the vent holes at the opposite end of the mold. This stresses the growing foam and allows for comparison of candidate polyols on the basis of area percent voids on the show surface of the foam pad. Data for the current study are presented in Figure 6.

Flowability, Area % Voids 40 Fail 10 Pass 9 8 Development Standard 7 6 5
Flowability, Area % Voids
40
Fail
10
Pass
9
8
Development Standard
7
6
5
4
4
3
2
1
1
0
Control
Control
Polyol C
At Full
At 50%
At 50%
Catalysts
Catalysts
Catalysts

Figure 6. Comparative flowability performance.

In this test, the control foam with the full level of added catalysts performs well below our internal development standard of no more than 10 area percent voiding. Drop- ping the catalyst levels of the control foam by 50% resulted

in the formation of voids over forty percent of the foam’s show surface. Active Polyol C at a 50% reduced catalysts loading performed better than the fully catalyzed control.

Vent Stability

Another common location for voids in a molded foam pad are those areas immediately below or adjacent to the vent devices. The data in Figure 7 were obtained by inspection and measurement of voids appearing below the vent holes in a simple 38.1 x 38.1 x 11.4 cm (15 x 15 x 4.5 in) heated test block mold. The vents for that mold were 1.6 millime- ters (1/16 inch) in diameter and were arranged in a tradi- tional five-hole pattern on the lid of the mold.

Vent Collapse, cm² per vent 24 58 Rise Time, sec. 26 10 9 Development Standard
Vent Collapse, cm² per vent
24
58
Rise Time, sec.
26
10
9
Development Standard
8
7.2
7
6
Fail
5
4.2
Pass
4
3
2.3
2
1
0
Control
Control
Polyol C
At Full
At 50%
At 50%
Catalysts
Catalysts
Catalysts

Figure 7. Polyol C vent stability results.

The development standard we use is that no foam formula- tion should demonstrate more than 5 square centimeters of void area per vent. Above this level, the voids become eas- ily detectable without cutting into the foam. For the present study, the control foam at full catalysis just meets this crite- rion. At the 50 percent reduced catalysts level, the control formulation is well into the unacceptable range of perform- ance. Active Polyol C shows an improved level of per- formance.

Also shown in this figure are the rise or mold fill times for each formulation. This number was recorded as the time for the first extrusion to be visible through the center vent hole. Twenty-four seconds is very typical for the fully catalyzed control formulation and that is matched nicely by the for- mulation containing Active Polyol C. The practical concern here is that any new formulation component not cause a faster rise time since most commercial foam plants have some limitations on how fast a mold lid can be closed and locked. Also, the rise time should not be so slow as for the other control formulation, so that the foam won’t still be rising (and still be weak) as the molds go bumping along down the conveyor line.

Foam Tightness

The overall moldability of a foam is often said to be better with a tight formulation than a more open one. One conse- quence of running a tight formulation is the danger of foam shrinkage if the cell-walls are not adequately opened in a foam crushing event. The concern here is that the foam survive that crushing event without losing physical dimen- sions or bursting apart. If the foam is too tight, the internal stress forces during crushing may exceed the tensile strength of the fresh foam resulting in a physical splitting apart of the foam pad as it goes through the crushing de- vice. This gross splitting results in a foam pad that must be scrapped. Comparison of relative shrinkage and force-to- crush performances are often useful in the development of new molded foam technologies.

Shrinkage

Our test scenario for measuring shrinkage in a standard test block of molded foam is illustrated in Figure 8.

test block of molded foam is illustrated in Figure 8. Figure 8. Shrinkage testing. In this

Figure 8. Shrinkage testing.

In this test, foams are prepared in the normal manner, care- fully removed from the mold and allowed to stand uncrushed overnight. The foam pad is then cut through the area of maximum vertical shrinkage, measured for mini- mum thickness and a percent shrinkage number calculated. Comparative data for the present work is presented in Fig- ure 9.

Shrinkage, %

70

60

50

Development Standard

in Fig- ure 9. Shrinkage, % 70 60 50 Development Standard Fail 50 40 30 20

Fail

50

40

30

20

10

20

Pass

27

0 Control

At Full

Catalysts

Control

At 50%

Catalysts

Polyol C

At 50%

Catalysts

Figure 9. Comparative shrinkage performance.

At the full catalyst levels, the control formulation performs at a shrinkage level that we consider to be an upper limit. With numbers above 50%, we have found that some com- mercial foamers have trouble running thicker foam pads through their crushing equipment. Shrinkage performance of experimental Active Polyol C is quite acceptable.

Force-To-Crush

A useful laboratory test for comparing relative foam tight- ness is the so-called Force-to-Crush test. Our version of this test scenario is illustrated in Figure 10.

version of this test scenario is illustrated in Figure 10. Figure 10. Force-to-crush test. In this

Figure 10. Force-to-crush test.

In this procedure, a foam is prepared in the normal manner, cured for the desired time and then removed from the mold (usually the standard test block mold) with care. The uncrushed foam pad is then quickly placed in the force measuring machine and deflected to 50% of its original thickness. Initial peak load and load decay are the basic data available. Figure 11 presents the initial peak load data for the present study. Foam based on the Active Polyol C falls nicely between the two control foams and all foams tested were well below any level of concern.

Force-To-Crush, N/323 cm 2 1,200 Fail 1,000 Pass 800 667 Development 467 Standard 600 400
Force-To-Crush, N/323 cm 2
1,200
Fail
1,000
Pass
800
667
Development
467
Standard
600
400
147
200
0
Control
Control
Polyol C
At Full
At 50%
At 50%
Catalysts
Catalysts
Catalysts

Figure 11. Comparative force-to-crush results.

Cure

For a new polyol to be commercially viable, it must con- tribute to an adequate level of foam cure at several critical points in the manufacturing process. Table 9 presents some practical examples of why foam cure is an important per- formance feature.

Table 9. Practical examples of foam cure.

Judged At

Affecting

Mold Fill

Bulk Stability and Flash

Part Demold Station

Green Strength and Fingerprinting

Crusher Station

Hot Set

Shipping Station

Short Term Static Fatigue

The extent of cure at the moment of mold fill directly af- fects the amount of polymer that escapes the mold through the venting devices and parting line. If this is excessive, valuable material is wasted and additional pad trimming and cleanup labor may be needed.

At the demold station, the foam must have enough green strength to resist tearing and fingerprinting due to human handling. These imperfections can usually be repaired off- line at some additional expense.

Another measure of cure comes after the foam leaves the

crushing device. A poorly cured foam may densify and lose

a few millimeters of its height dimension. Wrinkles may

also appear on the exterior of the pad, further detracting from its cosmetic appearance. Similar events may occur at the shipping station when multiple pads are compressed into a shipping container for delivery to the seat assembly plants. A foam with inferior cure may exhibit a permanent loss in physical dimensions when removed from such ship- ping containers. The cure testing scenario used for this work is shown in Figure 12.

Pour Cure Demold
Pour
Cure
Demold

Figure 12. The hot set cure test.

In this test, foam pads made in the normal way are dis-

pensed into a 38.1 x 76.2 x 6.3 cm (15 x 30 x 2.5 in) heated mold. After a 6 minute cure cycle, the foam pad was de- molded and immediately roller crushed at a gap setting of 1.27 cm (1/2 in). The pad was then placed in the indenter jig where four indenter feet regionally deflect the foam to various residual thicknesses. Four replicate pads are tested

at different deflection times and a final cumulative percent

hot set calculated. Data for the present study are presented in Figure 13.

Cure, % Hot Set 600 Fail 500 Pass 400 Development 300 267 240 200 145
Cure, % Hot Set
600
Fail
500
Pass
400
Development
300
267
240
200
145
100
0
Control
Control
Polyol C
At Full
At 50%
At 50%
Catalysts
Catalysts
Catalysts

Figure 13. Comparative cure performance.

The control foam based on the high-functionality polyol, SPECFLEX NC 630 at a full catalyst level shows its typi- cal outstanding cure performance. Lesser, but still very adequate, levels of cure were seen with reduced catalyst levels in both the control and Active Polyol C based foams.

Foam Physical Properties

All foam pads were thoroughly tested for physical proper- ties according to G.M. test methods. Of particular interest are the load-bearing and compression set performances of the new Active Polyol C versus the control foams. Data comparing the 65% IFD (indentation force deflection) per- formance are presented in Figure 14.

65% IFD, N/323 cm 2 500 367 400 342 327 Typical Performance 300 200 100
65% IFD, N/323 cm 2
500
367
400
342
327
Typical Performance
300
200
100
0
Control
Control
Polyol C
At Full
At 50%
At 50%
Catalysts
Catalysts
Catalysts

Figure 14. Comparative loadbearing performance.

Foams of this density grade and copolymer polyol level will generally give a 65% IFD in the range of 300 New- tons. Reducing the catalyst levels in the control foam gave the expected increase in loadbearing. Foams based on the new Active Polyol C were approximately 5% harder than the fully catalyzed control foam.

Compression set data are presented in Figure 15. The fig- ure shows the results for testing both the regular and the humid aged 50% C d set. These foams fall within the Gen- eral Motors Class C foam group and the typical specifica-

tion values shown are taken from General Motors Engineering Standards Document GM6293M.

50% C d Compression Set, %

 

50

 

65

 

93

 

Airflow, l/min

54

 
 

Regular Set   

 

40

Humid Aged Set40

 

Typical Spec for

Fail

30

Humid Aged Set

Pass

20

 

17

Fail

Typical Spec

16

 

15

  15   13 Pass for Reg Set 12  
 

13

Pass

for Reg Set

12

  15   13 Pass for Reg Set 12  
 

10

   

10

10     10  
 
       

0

Control

 

Control

 

Polyol D

 

At Full

At 50%

At 50%

 

Catalysts

Catalysts

 

Catalysts

Figure 15. Compression set performance.

Historically, compression set specifications have been among the most difficult to meet. All three foam systems easily met the requirements of both the regular and humid aged specifi- cations. Considering that compression sets usually respond to improvements in airflow, it seems logical that even better performance for the Active Polyol C based foams will be pos- sible with formulation fine tuning.

The remaining foam physical properties were consistent with those expected for a 32 kg/m 3 (2.0 lb/ft 3 ) core density molded foam based on TDI. Figure 16 presents a summary of foam physical properties wherein the performance of the Active Polyol C based foam is compared to that of the fully catalyzed control foam.

Foam Properties Worse Same Better Loadbearing Regular CS 5 20 Humid Aged CS Tensile Tear
Foam Properties
Worse
Same
Better
Loadbearing
Regular CS
5
20
Humid Aged CS
Tensile
Tear
Elongation
Resiliency
Airflow
6
7 *
8
17
* Still 150%
Above specification
-25 -20 -15 -10
-5
0
5
10
15
20
25
Percent Change Relative To Control

Figure 16. Performance features of active polyol versus fully catalyzed control foam.

In this format, the data is intended to show, for example, that both compression sets are improved, as is the tear strength. The tensile strength of the experimental foam was 7% worse than the control but both foam systems were at least 150% over the minimum specification requirement for foams of this density. Elongation and resiliency performances were identical. Airflow in the experimental foam was 17% lower indicating a need for further formulation fine tuning. This formulation work is underway and current developments are confirming that total elimination of bis- (2-Dimethylaminoethyl) ether, causing halovision (7), should be feasible.

CONCLUSION

The present paper has demonstrated that amine emissions can be drastically reduced and even eliminated from flexi- ble polyurethane foams through the use of new Dow active polyols combined or not with reactive catalysts.

Further development of active polyols and adjustment of formulations are underway at Dow with the aim to give several options to the polyurethane industry to eliminate amine emissions. Volatile and odor tests, not reported here, are being carried out routinely to make sure these programs are giving the desired outcomes.

The next step is the reduction of other volatile and fogging components in overall formulations in order to support the polyurethane industry’s strive to very low emissions and to meet new stringent OEM’s specifications.

ACKNOWDLEGEMENT

The authors wish to thank their many Dow colleagues who had a role in generating the data presented in this paper. Special thanks are extended to Alain Bleton, Lance Coo- per, Richard Elwell, Olga Milovanovic, Chris Noakes, Olivia Renevey, Alan Schrock, Mark Sonnenschein, An- toine Storione, Ross Polk, Eve Taylor, Mary White, and the Meyrin and Freeport foam testing laboratories person- nel.

BIBLIOGRAPHY

1. Broos R.; Casati F.M.; Herrington R.M.(1999), “En- durance of Polyurethane Automotive Seating Foams under Varying Temperature and Humidity Condi- tions”, Journal of Cellular Plastics, Volume 36 – May 2000, 207-245

2. Casati F.M.; Broos R.; Herrington R.M. ; Miyazaki Y. (1997), “Tailoring the Performance of Molded Flexi- ble Polyurethane Foams for Car Seats”, Proceedings of the 1997 SPI Polyurethane World Congress”, Tech- nomics: Lancaster, PA., 402-420

3. Casati F.M.; Herrington R.M.; Broos R. ; Miyazaki Y.; Phan Thanh H and Cadolle D.; (1998) “Automotive Seating Foams: Improving their Comfort and Durabil- ity Performance”, “Proceeding of Polyurethane the 1998 SPI Polyurethane conference”; Technomics:

Lancaster, PA., 417-431

4. Williams K.P.; J. Gerrard, D.L. “The Degradation of Poly(Vinyl Chloride) Studied using Fourier-Transform Ramam Spectroscopy” (1990), Eur. Polym. J., 26 (12)-

1355-8

5. Wilson A.S.; Gerrard D.L.; Bowley H.J. “Problems of Interaction Between Plasticised PVC and Polyurethane Foam” (1987). Presented at PVC’ 87, Brighton, UK., April 1987

6. Christfreund A.; Huygens E.; Eling B. “Amine-Free Catalyst Systems for Automotive Instrument Panels” (1991), Proceedings of Polyurethane World Congress, Technomics: Lancaster, PA., 272-277

7. Polyurethane Amine Catalysts: Guidelines for Safe Handling and Disposal; Technical Bulletin AX173, November 2000; Alliance for the Polyurethane Ind- stry: Arlington, VA.

8. Dernehl C.U. (1966), “Health Hazards Associated with Polyurethane Foams”, Journal of Occupational Medi- cine, 8/2, 59-62

9. Belin L.; Wass U.; Audunsson G. and Mathiasson L. (1983), “Amines: Possible Causative Agents in the Development of Bronchial Hypperreactivity in Work- ers Manufacturing Polyurethanes from Polyisocya-

nates”, British Journal of Industrial Medicine, 40, 251-

257

10. Bugler J.; Maddison P.; Hope S.J.; Mills I.G.; Nutt A.R. and Wright M.D. (1992) Tertiary Amine and Ethanolamine Catalysts in the Polyurethane Foam In- dustry: New Methods of Detection and Results of Per- sonal Sampling in Nine UK Flexible Foam Factories”, Cellular Polymers, 11/3, 171-200

11. Reed D. (1999), “VW aims to cut amines”, Urethanes Technology, 16/4, 3

12. Boinowitz T.; Burkhart G.; Schloens H.H. (1999) “Emanations from Flexible Slabstock Foams – Signifi- cant Reduction of Emissions is Now Possible”, Pro- ceeding of Polyurethanes Expo 99; Technomics:

Lancaster, PA., 283-287

13. Zimmerman R.L.; Renken T.L. (1988): “Low Odor Reactive Amine Catalysts for Polyurethane Foams”, Proceedings of the SPI-31 st Annual Techni-

cal/Marketing Conference, Technomics: Lancaster, PA., 36-40

14. Mercando L.A.; Kniss J.G.; Tobias J.D.; Plana A.; Listemann M.L.; Wendel S.; “Non-Fugitive Catalysts for Flexible Polyurethane Foams”, (1999) Proceeding of Polyurethanes Expo 99; Technomics: Lancaster, PA., 103-134

15. Kometani H; Tamano Y.; Masuda T.; Van Maris R.; Gay K.; (2000) “The Investigation of Amine Emis- sions from Polyurethane Foam”; Proceeding of Polyu- rethanes Conference 2000; Technomics: Lancaster, PA., 11-21

16. Rothe J.; Cordelair H.; Wehman C.; (2000) “New Catalysts for Low VOC in Flexible Slabstock Foam”, Proceeding of Polyurethanes Conference 2000; Tech- nomics: Lancaster, PA., 109-116

17. Sikorski M.; Wehman C.; Cordelair H. (1999) “New Additive Solutions for Low VOC in HR Molded Foams”. Proceedings of Polyurethanes Expo 99; Technomics: Lancaster, PA., 135-144

18. Mapleston P; “Riding Comfort is a Focus of Automo- tive Foam Systems” (2001), Modern Plastics, March 2001, 30-31

19. Broos R.; Sonney J.M.; Phan Thanh H.; Casati F.M.; (2000) “Polyurethane Foam Molding Technologies for

Improving Total Passenger Compartment Comfort”, Proceedings of the Polyurethane Conference 2000, Technomics: Lancaster, PA., 341-353

20. Malwitz N.; Manis A.; Wong S.W.; Frisch K.C.; (1986) “Amine Catalysis of Polyurethane Foams”, Proceedings of the 30 th Annual Polyurethane Techni- cal/Marketing conference, 1986, Technomics: Lan- caster, PA., 338-353

21. Nutt A.R.; Skidmore D.W. (1987) “Recovery of Chlo- rofluorocarbon 11 by Activated Carbon Scrubbing on a Polyurethane Foam Slabstock Plant”, Cellular Poly- mers, Volume 6, 1987, 62-77

22. Herrington, R., De Genova, R., Casati, F. and M. Brown (1997), “Molded Foams, Chapter 11”, In Flexible Polyurethane Foams; Herrington, R. and K. Hock, eds., The Dow Chemical Company, Form No. 109-01061, 11.1-11.41

23. Herrington R.M. and Klarfeld D.R. (1983) “Humid Aged Compression Set Phenomena in All Water Blown HR Molded Foams”, Proceedings of the 1983 SPI Polyurethanes Conference, Technomics: Lancas- ter, PA., 177-182

24. Brasington R. and De Roeck H. (2000) “Accelerated Testing for Durability Performance of Automotive Seating Foam”, Proceedings of the API 2000 confer- ence, Technomics: Lancaster, PA., 267-279

BIOGRAPHIES

François M. Casati

François 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 a Product Development Leader, R&D, for the Flexible Foam business of Dow.

Leader, R&D, for the Flexible Foam business of Dow. Ronald M. Herrington Ron Herrington is a

Ronald M. Herrington

for the Flexible Foam business of Dow. Ronald M. Herrington Ron Herrington is a Development Associate

Ron Herrington is a Development Associate in the Polyurethane Products Technical Service and Development Laboratory of The Dow Chemical Company in Texas. He received a Bachelor’s Degree in Chemistry from the University of Houston in 1970. He joined Dow in that year and has since gained wide experience in the fields of slabstock and molded flexible foams.

Jean-Marie Sonney

Dr. Jean-Marie Sonney graduated from the Swiss Federal In- stitute 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 these years, he had various responsibilities in the field of Analytical Chemistry, Quality Assurance, EH&S and Quality Management. He is currently a project engineer in the Development Group for Molded Foams and Specialties with responsibilities for NVH applica- tions.

Specialties with responsibilities for NVH applica- tions. Johnson Tu Johnson Tu is a Sr. Development Specialist

Johnson Tu

with responsibilities for NVH applica- tions. Johnson Tu Johnson Tu is a Sr. Development Specialist in

Johnson Tu is a Sr. Development Specialist in the Research and Development Group of The Dow Chemical Company in Freeport, Texas. He received a BS Science from the Chengkun University in Taiwan in 1983. He joined Dow in 1990 and has held several positions in R&D/TS&D and new Business Development.

Henri Mispreuve

Dr. Henri Mispreuve graduated from the State University of Mons (Belgium) in 1975 and received his Ph.D. in Physical Organic Chemistry from the same University in 1979. In 1984, he joined Dow Europe S.A. in Horgen (Switzerland). He is currently responsible for Technical Service and Development of Polyurethane Slabstock Foams at the company’s International Development Center in Meyrin/Geneva (Switzerland).

Development Center in Meyrin/Geneva (Switzerland). Alain Fanget Alain Fanget joined the Geneva-based
Development Center in Meyrin/Geneva (Switzerland). Alain Fanget Alain Fanget joined the Geneva-based

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 moulding and ACES applications. He is currently a Technical Service Specialist in the Automo- tive Thermosets R&D Group of the Meyrin International De- velopment Center, with specific responsibilities in seating and NVH moulding applications.

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

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