CATALYZING GREEN CHEMISTRY
Rigid Panel Foams with Unique Properties from
CO2-based Polyols
Anna Cherian, Chris Fordice, Kimberly Jaskula, Mike Nagridge,
Simon Waddington, Wayne Willkomm
UTECH North America
June 2014
Charlotte, NC
CATALYZING GREEN CHEMISTRY
Novomer’s technology: Direct conversion of
waste CO2 to useful products
2
CATALYZING GREEN CHEMISTRY
Polycarbonate Polyols from CO2
O
+
CO2 Unique characteristics of the new polyol technology
Distinctive performance from the high density carbonate backbone
Economically attractive due to the use of inexpensive & readily available CO2
Strong sustainability story due to direct sequestering of CO2 in backbone
3
CATALYZING GREEN CHEMISTRY
A wide range of starting molecules can be used
Fn = 2
Examples of starters used to create PPC polyols
OH
H O
n
Fn > 2
HO
OH
O
O
O
OH
HO
HO
O
O
O
O
OH
HO
4
CATALYZING GREEN CHEMISTRY
Polycarbonate Polyol
Polycarbonate polyols are clear,
amorphous, viscous liquids.
Hydroxyl termination reacts in
equivalent manner to any
commercial polyol.
Polyurethanes containing
polycarbonate polyols have
excellent chemical, UV, oxidative
and hydrolytic resistance.
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CATALYZING GREEN CHEMISTRY
These precise polycarbonate polyols enhance the
strength of polyurethane products
Tensile strength of TPUs based on
Novomer and other polyols
Characteristics of Novomer polyols
100% polycarbonate backbone:
perfectly alternating CO2 / epoxide
units yielding 100% carbonate and
zero ether linkages
12
Psi (thousands)
10
Perfect -OH functionality: diols are
2.0 functional & triols are 3.0
functional at any molecular weight;
no unsaturation
Precise control of molecular weight:
any Mw from ~500 g/mol to 10,000+
g/mol, all with a polydispersity index
(PDI) of ~1.1
8
6
4
2
0
PPC
Polyol
6
Exist.
PCDs
Ester
Polyol
CATALYZING GREEN CHEMISTRY
™
The convergence of Performance, Cost, and Sustainability
212-10 : This is a 1,000 Mw diol from propylene oxide and
CO2, OH# = 112, 39% mass from CO2
212-20 : This is a 2,000 Mw diol from propylene oxide and
CO2, OH# = 56, 41% mass from CO2
Commercial quantities available in mid-June 2014
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CATALYZING GREEN CHEMISTRY
Rigid Foam Formulations
B-side
EW
PPC 1000 Mw diol
Stepanpol PS 2352
Water
Fyrol PCF
E-AF084
E06-16
Pentane
Polycat 46
Polycat 5
Dabco SI3201
Lupranate M20
Index
505
234
9
187
50
135
1
Parts
50
50
0.4
10
0
0
14
5
0.2
2
231
375
8
2
3
4
5
6
50
50
0.4
0
0
0
14
5
0.2
2
231
375
0
100
0.4
10
0
0
14
5
0.2
2
289
375
0
100
0.4
0
0
0
14
5
0.2
2
289
375
50
50
0.4
0
10
0
14
5
0.2
2
231
375
50
50
0.4
0
0
10
14
5
0.2
2
258
375
CATALYZING GREEN CHEMISTRY
Rigid Foam Blocks
PPC/PS 2352
PCF
no FR
Density: 1.50
1.64
PS 2352 (controls)
PCF
no FR
2.58
2.56
PPC/PS 2352
E-AF084
E06-16
1.48
Rigid foams made with PPC have shown significantly
lower density than control foams
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1.64
CATALYZING GREEN CHEMISTRY
Blowing Efficiency
2.1
Density (pcf)
2
1.9
1.8
1.7
1.6
5
10
15
20
Pentanes (parts)
Control foams yield 2.5 pcf at 14 parts pentane
This can be valuable for high performance blowing agents such as HFC 245fa
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CATALYZING GREEN CHEMISTRY
Dimensional Stability
1 Wk: Dimensional Stability (%)
1
2
3
4
5
6
Δ Wt
-3.94
-3.37
-0.04
-0.43
-3.63
-1.68
Δ L (Sides 1 & 3)
1.61
-0.71
0.72
0.54
-0.23
1.65
Δ W (Sides 2 & 4)
2.66
-0.45
0.57
0.77
0.17
2.36
Δ L&W (All 4 Sides)
2.13
-0.58
0.64
0.66
-0.03
2.01
ΔH
-1.05
-0.42
0.26
-0.63
-1.62
-0.99
Dimensional Stability for 1 week at 200˚F
Dimensional Stability is acceptable for controls and PPC samples 2 (with Fyrol PCF)
and 5 (experimental FR), despite very low density of 1.64 and 1.48, respectively
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CATALYZING GREEN CHEMISTRY
Cone Calorimeter - Controls
120
HRR (kW/m2)
100
80
HRR-3A
HRR-3B
60
HRR-3C
40
20
0
0
20
40
60
80
100
120
140
160
180
Time (seconds)
3 replicates of control formulation, 100% Stepanpol, with 10% Fyrol PCF
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CATALYZING GREEN CHEMISTRY
Cone Calorimeter - PPC
120
HRR (kW/m2)
100
HRR-1A
HRR-1B
HRR-1C
80
60
40
20
0
0
20
40
60
80
100
120
140
160
180
Time (seconds)
3 replicates of formulation with 50% PPC:50% Stepanpol and 10% Fyrol PCF
PPC enables faster extinguishing and less total heat release
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CATALYZING GREEN CHEMISTRY
Cone Calorimeter Summary
600
Total Heat (MJ/m2)
500
Peak HRR (kW/m2)
Total Smoke (m2/m2)
400
Mass Loss (wt%)
300
200
100
0
1
2
PPC
3
4
Control s
14
5
6
PPC w/experimental FR
CATALYZING GREEN CHEMISTRY
Total Heat Release
80
Total Heat (MJ/m2)
Mass Loss (wt%)
70
60
50
40
30
20
10
16.7
11
8.8
10
9.7
10
0
1
2
PPC
3
4
Controls
15
5
6
PPC w/experimental FR
CATALYZING GREEN CHEMISTRY
Formulation Summary
B-side
OH #
111
PPC 1000 Mw diol
PS 2352
240
Fyrol PCF
E-AF084
E06-16
300
Aromatic Content
Density (pcf)
1
2
3
4
5
6
Parts
50
50
0
0
50
50
50
50 100 100
50
50
10
0
10
0
0
0
0
0
0
0
10
0
0
0
0
0
0
10
40% 41% 45% 46% 40% 41%
1.50 1.64 2.58 2.56 1.48 1.64
PPC containing Rigid foams have similar flammability
results, with lower density and lower aromatic content
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CATALYZING GREEN CHEMISTRY
Novomer Polyols have lower Heat of Combustion
Heat of Combustion (MJ/kg)
35
30
Up to 50%
lower Fuel
Value
25
20
15
10
Rigid polyether
Flexible
polyether
Mannich polyol
Aromatic
polyester
Lower heat of combustion - one of the carbons is already
fully oxidized. This is a fundamental characteristic of
Novomer polycarbonate polyols.
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Polypropylene Polyethylene
carbonate
carbonate
n
CATALYZING GREEN CHEMISTRY
Cannon Machine Trials
Cannon has 3 stream, high pressure, multipurpose machine
This machine was used to prepare flexible and rigid foams, and
aliphatic polyurethane clear coats
One stream is heated, allowing the use of higher viscosity
components
A blend of 70% PPC and 30% Stepanpol PS 2352 was used to
deliver the PPC polyol
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CATALYZING GREEN CHEMISTRY
Reduced Viscosity Blends
20000
DBE-3
Diexter G 1100-112
Propylene Carbonate
PPG 425
Stepanpol PS 2352
TCPP
Voranol 270
10000
9000
8000
7000
6000
5000
Viscosity (cP)
4000
3000
2000
A number of different
components can be
used to blend with PPC
and reduce the viscosity
1000
900
800
700
600
500
400
300
200
55
60
65
70
75
80
85
Weight % PPC
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90
95
100
CATALYZING GREEN CHEMISTRY
Cannon Trial Foam w/25% PPC
Average cell size is 143
microns (per ASTM D3576)
High closed cell content was
not achieved, so k factor was
greater than expected.
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CATALYZING GREEN CHEMISTRY
Cannon Trial Foam w/50% PPC
Average cell size is
169 microns (per ASTM
D3576)
50% PPC foam was run
hotter, and had some
scorching
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CATALYZING GREEN CHEMISTRY
Commercial Benchmark
Commercial benchmark has
average cell size of 241 microns
(per ASTM D3576) and measured
by the same laboratory
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CATALYZING GREEN CHEMISTRY
Conclusions
Rigid polyisocyanurate foams can readily be made with PPC
polyol.
Rigid foams using PPC have demonstrated better blowing
efficiency and smaller cell sizes.
Blends can be used to produce a workable viscosity.
PPC polyols have a lower heat of combustion which can
translate to reduced flame retardant requirements.
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CATALYZING GREEN CHEMISTRY
Future Work
Optimize the polyisocyanurate formulation to take advantage
of the features that the CONVERGE™ polyols offer
Fully characterize the foam systems with respect to:
•
•
•
•
•
•
k factor
Dimensional stability
Polymer rigidity
Closed cell content
Reduced moisture uptake
Reduced heat of combustion
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