C.T. Thurau, A. R. Arnold, T. Panitzsch

CPI Technical Conference, September 2012

Reducing Silicone Surfactant

Emissions in Flexible Molded

Foam

© Air Products and Chemicals, Inc. 2012

Presentation Overview

Focus on Emissions

Dabco “SI” Reduced Emission Surfactants

TDI/MDI Molded Foam Evaluations: Cell Structure and Force-to-Crush

Physical Properties

Emissions Results

MDI Molded Foam Evaluations: Force-to-Crush

Physical Properties

Emissions Results

Product Benefits and Conclusions

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Focus on Emissions

Awareness regarding the safety and environmental impact of Flexible PU foam has significantly increased since 2000.

Today, numerous emissions specifications and tests exist in the automotive industry

VDA 278 SAE J1756-06

VDA 270 PV 3937

VDA 276 GMW 15634

…others

Air Products’ reduced emission silicone surfactants for flexible molded foam applications can help you meet OEM specifications

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Why Should YOU be

Concerned with Emissions?

Numerous production and end-product performance issues can be linked to PU foam emissions.

Odor VOCs

Fogging PVC Staining

Worker Exposure Production Safety

Toxicity from targeted substances

Low Emissions are becoming a requirement of sale for many automotive OEMs

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What Causes Emissions?

Many components in PU foam are responsible for emissions, including silicone surfactants

As a leading supplier of these surfactants, Air Products continues to develop solutions to address emissions concerns.

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Designing a Reduced Emission

Surfactant

Many approaches can be utilized to reduce surfactant emissions:

Isocyanate reactive groups

Increased silicone efficiency

Functionalized carriers

Stripping of by-products and contaminants

Our Dabco SI Surfactants combine these approaches

Reduced Emissions

(per VDA278, SAE J1756, others…)

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Flexible Molded Surfactants:

Reducing Emissions

MDI

Cell Regulation

Dabco DC2525 / *Dabco SI1101

Surface Regulator

Dabco DC2585

High Efficiency Regulator

High Density Molded

Dabco DC5160

Stabilization and Pinhole Reduction

TDI

Balanced Product

Dabco DC6070

Regulation and stabilization

Extend Processing Latitude with two co-surfactants

Dabco DC5179 / *Dabco SI1301

Cell Regulator

Dabco DC5164 / *XF-AA15004

Strong Bulk Stabilizer

Dabco DC5043

Medium Bulk Stabilizer

* Denotes new reduced emission offerings

Formulation Identifier A B C D

Conventional Polyol, [pphp] 80 80 80 80

SAN Co-polymer Polyol, [pphp] 20 20 20 20

Dabco DEOA-LF, [pphp] 1.5 1.5 1.5 1.5

Dabco 33LX, [pphp] 0.32 0.32 0.32 0.32

Dabco BL-11, [pphp] 0.08 0.08 0.08 0.08

Total Water, [pphp] 3.9 3.9 3.9 3.9

Dabco DC5179, [pphp] 0.6 0.6

Dabco DC5164, [pphp] 0.2 0.2

Dabco SI1301, [pphp] 0.6 0.6

XF-AA15004, [pphp] 0.2 0.2

TDI/MDI Molded Foam

Evaluations: 32kg/m3

Pilot-scale machine trials investigated various TDI/MDI systems.

The performance of Dabco SI1301 and XF-AA15004 was compared to Dabco DC5179 and Dabco DC5164

8 surf

acta

nts

TDI/MDI Molded Foam:

Force-to-Crush

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Dabco SI1301 and XF-AA15004 offer the same excellent open cell structure as the control surfactants

0

50

100

150

200

250

300

0 1 2 3 4 5 6 7 8 9 10

Fo

rce

, N

/cm

2

Frequency

0.6 Dabco DC51790.2 Dabco DC5164

0.6 Dabco SI13010.2 Dabco DC5164

0.6 Dabco DC51790.2 XF-AA15004

0.6 Dabco SI13010.2 XF-AA15004

TDI/MDI Molded Foam:

Cell Structure

Dabco SI1301 and XF-AA15004 generate the same fine surface and bulk cell structure as the industry standard surfactants

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Control

0.6 pphp Dabco DC5179 0.2 pphp Dabco DC5164

Reduced Emission

0.6 pphp Dabco SI1301 0.2 pphp XF-AA15004

TDI/MDI Molded Foam:

Physical Properties

Dabco SI1301 and XF-AA15004 show comparable physical properties to the control

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Property

ASTM-D3574

Dabco DC5179 /

Dabco DC5164

Dabco SI1301/

Dabco DC5164

Dabco DC5179/

XF-AA15004

Dabco SI1301/

XF-AA15004

Core Density, (kg/m3) 32.1 31.6 31.6 32.2

Air-Flow, (L/m) 71.5 70.5 79.4 83.1

25% ILD, (N) 79 81 84 91

65% ILD, (N) 284 277 272 290

25% R ILD, (N) 68 68 71 77

Support Factor 3.6 3.4 3.2 3.2

Ball Rebound, (%) 62 58 56 62

Tensile Strength, (kPa) 104.8 110.6 103.4 103.5

Elongation, (%) 92.6 91.9 93.9 103.5

Tear Strength, (N/m) 165.2 166.3 169.8 173.1

50% Dry Comp. Set, (%) 5.3 4.7 4.6 3.8

50% Jap. Wet Set, (%) 31.3 32.2 28.8 25.7

Inert Gas

Thermal Desorption Tube

90oCCryogenic Trap

(-150oC)

VOC

Cryogenic Trap

(-150oC)

FOG120oC

Foam

Inert Gas

Industry Emissions Testing:

VDA278

Thermal desorption test method (Dynamic Headspace) frequently used by the automotive industry

VDA278 gives data relating to emissions in the final foam product

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Recent Changes to the VDA 278

Testing Methodology

In November 2011, changes were made to the existing VDA 278 test that resulted in more emissions being detected

VOC detection extended up to C25 n-alkane elution range

FOG detection range lowered to C14 n-alkane

elution range

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C20

C25

VOC 90 °C

C14

C16 C32 FOG 120 °C

Variables in Emissions Testing

Many variables can impact the emissions remaining in the foam:

Foam Density / Foam Exotherm

Foam Airflow / Open Cell Content

Foam Index

Ventilation

Cure Duration

Transportation Conditions

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Dabco DC5179 /

Dabco DC5164

Dabco SI1301/

Dabco DC5164

Dabco DC5179/

XF-AA15004

Dabco SI1301/

XF-AA15004

VDA 278 VOC Results

Total VOC 1335 719 1221 475

Siloxane VOC 307 191 243 136

VDA 278 FOG Results

Total FOG 327 216 225 168

Siloxane FOG 11 7 4 11

Combined Emission Results

TVOC + TFOG 1662 935 1446 643

VOCsilox + FOGsilox 318 198 247 147

TDI/MDI Emissions Results:

VDA 278

Dabco SI1301 reduces TVOC by 46% and VOCsilox by 38% vs. Dabco DC5179. TFOG decreases by 35%

XF-AA15004 reduces TVOC by 10% and VOCsilox by 20% vs. Dabco DC5164. TFOG decreases by 30%

TDI/MDI Gravimetric Fogging

Results: SAE J1756-06

The combination of Dabco SI1301 and XF-AA15004 reduces Gravimetric Fogging deposits by 60% versus the control and improves Photometric results

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Dabco DC5179 /

Dabco DC5164

Dabco SI1301/

Dabco DC5164

Dabco DC5179/

XF-AA15004

Dabco SI1301/

XF-AA15004

Gravimetric Method

Weight of Fog

Deposit (mg) 0.75 0.30 0.75 0.35

Photometric Method

% Reflectivity 93 98 96 99

Observations Dry droplets,

no crystals

Dry droplets,

no crystals

Dry droplets,

no crystals

Dry almost

clear, no

crystals

Formulation Identifier E F

Conventional Polyol, [pphp] 100 100

Cell Opening Polyol, [pphp] 1.3 1.3

Dabco DEOA-LF, [pphp] 0.7 0.7

Dabco NE1070, [pphp] 0.9 0.9

Dabco NE300, [pphp] 0.2 0.2

Total Water, [pphp] 3.7 3.7

Dabco DC2525, [pphp] 1.0

Dabco SI1101, [pphp] 1.0

MDI Molded Foam

Evaluations: 45kg/m3

Machine trials conducted in European Technical Center

The performance of Dabco SI1101 was compared to the industry standard, low emission surfactant, Dabco DC2525

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MDI Molded Foam:

Force to Crush

Dabco SI1101 shows the same excellent open cell structure as Dabco DC2525

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MDI Molded Foam:

Importance of Cell Regulation

Without surfactant

1.0 pph Dabco DC2525

or Dabco SI1101

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MDI Molded Foam:

Physical Property Results

Dabco SI1101 generates excellent physical properties equivalent to those observed with Dabco DC2525

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Property* Dabco DC2525 Dabco SI1101

Core Density, (kg/m3) 41 41

Molded Density, (kg/m3) 45 45

CLD [kPa] 4.6 4.93

Tensile Strength [kPa] 141 139

% Elongation 115 103

*Tensile and Elongation: DIN EN ISO 1798 *50% CLD Method: ISO 2943

Dabco DC2525 Dabco SI1101

VDA 278 VOC Results

Total VOC 30 9

Siloxane VOC 26 8

VDA 278 FOG Results

Total FOG 274 261

Siloxane FOG 10 11

Combined Emission Results

TVOC + TFOG 304 270

VOCsilox + FOGsilox 36 19

MDI Emissions Results:

VDA 278

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70% lower VOC

Dabco SI1101 further improves upon the excellent emissions profile of Dabco DC2525

50% less Siloxane

MDI Gravimetric Fogging

Results: DIN 75201-R

DIN75201-R Process B utilized

– 100oC for 24 hours

While no significant differences in FOG were seen in VDA278 results, SI1101 showed 30% less deposits in Gravimetric Fog testing

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Dabco DC2525 Dabco SI1101

Gravimetric Method

Weight of Fog Deposit

(mg/g foam) 0.20 0.158

Product Benefits Summary

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Reduced Emission Cell Regulator, TDI

Fine cell structure with no

basal cells

40% Reduction in emissions vs. Dabco DC5179

Reduced Emission Bulk Stabilizer, TDI

Fine and open cell structure

Zero siloxane emissions in

VOC and FOG

Ultra-low Emission Cell

Regulator, MDI

Excellent cell structure and

phys. properties

70% lower VOC versus Dabco

DC2525

Dabco SI1301 Dabco XF-AA15004 Dabco SI1101

tell me more www.airproducts.com

Thank you

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