Reducing Silicone Surfactant Emissions in Flexible …... · C.T. Thurau, A. R. Arnold, T....
-
Upload
truongquynh -
Category
Documents
-
view
220 -
download
2
Transcript of Reducing Silicone Surfactant Emissions in Flexible …... · C.T. Thurau, A. R. Arnold, T....
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
2
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
3
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
4
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.
5
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…)
6
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
9
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
10
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
11
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
12
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
13
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
14
15
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
16
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
17
MDI Molded Foam:
Force to Crush
Dabco SI1101 shows the same excellent open cell structure as Dabco DC2525
18
MDI Molded Foam:
Importance of Cell Regulation
Without surfactant
1.0 pph Dabco DC2525
or Dabco SI1101
19
MDI Molded Foam:
Physical Property Results
Dabco SI1101 generates excellent physical properties equivalent to those observed with Dabco DC2525
20
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
21
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
22
Dabco DC2525 Dabco SI1101
Gravimetric Method
Weight of Fog Deposit
(mg/g foam) 0.20 0.158
Product Benefits Summary
23
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