from soybean oil to polyurethane flexible foams...polyurethane (pu) & research focus 1 ial...
TRANSCRIPT
From Soybean Oil to Polyurethane Flexible Foams
Ling Zhang
Advisor: Chris W. Macosko
Is Natural Oil an Alternative to Petroleum Oil?
Date: Sept. 5th, 2008
University of Minnesota, Minneapolis, MN
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
2
Sept. 5th, 2008
Acknowledgements
• Financial support:
• Collaborators: Tim Abraham, Jeff Malsam, Wei Zhang & BiOH labs (Cargill); Dave Henton, Ron Herrington; Mark Listemann, Gary Johnson (Air Products)
• Advisor: Chris Macosko & Committee members
• Prof. Tom Hoye & Hoye research group, Macosko Research Group & Polymer Group
• Undergraduate researchers: Kari Tanaka, Ryan Seelbach & Scott Dixon
• Machine shop, staff and administrative assistants
• Family & Friends
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
3
Sept. 5th, 2008
• Versatility– Range of products
• Elastomers, coating, adhesives, sealant • Rigid foams & Flexible foams
– Process methods• Casting, reaction injection molding, foaming, compounding…
• Research focus – Flexible foam– 40% of PU 1
– Wide range of applications– Room for innovation & challenging
Polyurethane (PU) & Research Focus
1 IAL consultants, 2004 End-use Market Survey on the Polyurethane Industry: 2005
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
4
Sept. 5th, 2008
PU Flexible Foam Chemistry
NCOOCNOCN
NCOOCN OCNNCO NCO
OH
OHHO
Polyol
Isocyanate (TDI)
OHH
Water
NCOOCN
O
OHHO
NCOCNO=
Hgelling reaction
O C N N C N N C
OO
HH
H
OH
+ O=C=O
blowing reaction
OO
O
O
OO C N
N C
N C
C N
C N C N
OO
HH
N C N
O
HH
N C N
O
HH
N C
O
HH
N
N C O
N C N
O
HH N C N
O
HH
N C O
H
O
N C O
O C N
O
O
H
H
H
O
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
5
Sept. 5th, 2008
PU Foam Morphology
Soft Domain
Hard Domain
Distinct Tg’s
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
O
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
O
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
O
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
O
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
Cooper, S. L.; Tobolsky, A. V., J. Appl. Poly. Sci., 1966 (10):1837
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
6
Sept. 5th, 2008
Motivation
OH
OHHO
NCOOCN
Polyol
Isocyanate (TDI)
OHH
Water
soybean
rapeseed
castor bean
linseed
oil
soybean
rapeseed
castor bean
linseed
oil
Soybean Oil 2: ~ 52 ¢/lb
Castor Oil 3: ~ 63 ¢/lb
2 CBOT, Sept. 4th, 20083 Chemical Market Reporter
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
7
Sept. 5th, 2008
Polyol vs. Natural Oil
O
O
O
O
O
O
O
O
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OH
OH
OH
O
O
OO
OO
OO
OO
OO
OO
OO
OO
OH
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OH
OH
Polyether polyol (petroleum-derived)
Natural oil
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
8
Sept. 5th, 2008
Going from Natural Oil to Polyol
O
O
O
O
O
O
O
O
O
OR 2R 3
1O3
H2O
O
O
OOH
R2'R3'
OzonolysisO
O
O
OR2'R3'
OH
Microbial Conversion
2
4
O
O
O
OR2'R3'
OH
Hydroformylation
CO, H2
H2
MeOH
H2 O2…3
O
O
O
OR2'R3'
OH
O
Epoxidation
O
O
O
OR2'
R3'
N
N
OHOH
OHOH
5
NH
OHOH
I2Halogen addition + substitution
1 Petrovic ZS et.al., Biomacromolecules, 2005(6):7132 Hou CT, Adv. Appl. Microbio., 1995(41):1
3 Petrovic ZS et.al., US Patent 6,433,121; 20024 Dow Chemicals, WO Patent 2004096744 A2; 2004
5 Garrett TM, Du XX, US Patent Appl. 20080076901; 2008
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
9
Sept. 5th, 2008
We Have Natural Oil Polyols…Now What?
• Focus: flexible foam
O
O
O
OO
O
OH
OH
OH OH
OMe
OMe
OMe
OH
O
O
O
OO
O
OH
OH
OH OH
OMe
OMe
OMe
OH
SBOP
O
O
O
O
OH
OHO
O
Castor Oil
O
O
OO
OO
OO
OO
OO
OO
OO
OO
OH
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OH
OH
Hyperlite
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
10
Sept. 5th, 2008
Making the Foam
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
11
Sept. 5th, 2008
Not Quite Flexible ?!
1.0E+03
1.0E+04
1.0E+05
1.0E+06
1.0E+07
1.0E+08
-150 -50 50 150 250
Temperature (oC)
G' (
Pa) Hyperlite
Castor oil
SBOP
motor
transducerSerratedplates
ω
= 1 rad/s
25 °C
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
12
Sept. 5th, 2008
Why?!
O
O
O
OO
O
OH
OH
OH OH
OMe
OMe
OMe
OH
O
O
O
OO
O
OH
OH
OH OH
OMe
OMe
OMe
OHO
O
O
O
OH
OHO
O
Castor Oil
O
O
OO
OO
OO
OO
OO
OO
OO
OO
OH
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OH
OH
Hyperlite
SBOP
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
13
Sept. 5th, 2008
A Partial Polyol Component — SBOP
• Adding SBOP into flexible foams
– Hydrophobicity filler– Low molecular weight crosslinker polyol?*
O
O
OO
OO
OO
OO
OO
OO
OO
OO
OH
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OH
OHHyperlite
* high functionality, low molecular weight
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
14
Sept. 5th, 2008
Partially Substituted Foams• Filler: SAN-copolymer filled polyol
• Crosslinker: Voranol® 446
O
O
OO
OO
OO
OO
OO
OO
OO
OO
OH
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OH
OH
Crosslinker
SAN
O
O
OO
OO
OO
OH
OHOH
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
15
Sept. 5th, 2008
Partially Substituted Foams
• X: % of base polyol (Hyperlite) being substituted• Y: substituent polyol
– SAN– Crosslinker– SBOP
• Samples– Control – 30% SAN– 10% Crosslinker– 10% SBOP– 30% SBOP
X% Y
30% SBOP
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
16
Sept. 5th, 2008
Notably Harder Foams – 30% SBOP
0
5
10
15
20
control 30% SAN 10%crosslinker
10% SBOP 30% SBOP
Pres
sure
(kPa
)
10% Crosslinker
1mm
Control
30% SBOP
10% SBOP
30% SAN
0.3
0.6
0.9
1.2
1.5
control 30% SAN 10%crosslinker
10% SBOP 30% SBOP
Cel
l Dia
met
er (m
m)
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
17
Sept. 5th, 2008
Polymer Phase is Key
25 mm
10 mm
motor
transducerSerratedplates
ω
= 1 rad/s 3
3.5
4
4.5
5
5.5
6
-120 -70 -20 30 80 130 180Temperature (oC)
log
(G',
Pa)
10% Crosslinker 30% SAN
Control
113 oC
3
3.5
4
4.5
5
5.5
6
-120 -70 -20 30 80 130 180Temperature (oC)
log
(G',
Pa)
30% SBOP
10% SBOP
Control
0
5
10
15
20
control 30% SAN 10%crosslinker
10% SBOP 30% SBOP
Pres
sure
(kPa
) G’ @ 25oC
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
18
Sept. 5th, 2008
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
O
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
O
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
Hard Domain
Soft Domain Distinct Tg’s
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
O
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
O
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
Hard Domain
Soft Domain Distinct Tg’s
Is It the Tg of Soft Phase?
-120 -70 -20 30 80 130 180 230Temperature (oC)
Hea
t Flo
w (a
.u.)
Control
30% SAN
10% Crosslinker
10% SBOP
30% SBOPΔCp
Sample ΔCp (J/g/oC)
Control 0.33
30% SAN 0.25
10% Crosslinker 0.23
10% SBOP 0.16
30% SBOP 0.14
Serious loss of soft domain volume fraction?!
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
19
Sept. 5th, 2008
Where Did Soft Phase Go?• Phase mixing — less phase separated• Change of domain spacing
0.02 0.03 0.04 0.05 0.06 0.07 0.08
q (Å-1)
Nor
mal
ized
Inte
nsity
(a.u
.)
Control
30% SAN
30% SBOP
10% SBOP
10% Crosslinker
• 30% SAN– Increased
phase contrast• 10% crosslinker
– Reduced phase contrast
– Increased domain spacing
• SBOP – Reduced phase
contrast– Reduced
domain spacing
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
20
Sept. 5th, 2008
SAN
SAN
Crosslinker foam
SBOP foam
What Would That Look Like?
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
21
Sept. 5th, 2008
A Closer Look30% SAN 30% SBOPControl
1 x 1 μm 25o 2 x 2 μm 90o 1 x 1 μm 10o
500 x 500 nm 1 x 1 μm 500 x 500 nm
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
22
Sept. 5th, 2008
Partially Substituted Foams
• Potential and viable route
• SBOP makes harder foam– Different mechanism
• Change in hard domain morphology
• Partially substituted full potential
• Synthesize natural oil-based polyol– be used as the sole polyol component
500 x 500 nm 25°
500 x 500 nm 10°
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
23
Sept. 5th, 2008
Flash Back… High Tg = Rigidity
O
O
O
OO
O
OH
OH
OH OH
OMe
OMe
OMe
OH
O
O
O
OO
O
OH
OH
OH OH
OMe
OMe
OMe
OHO
O
O
O
OH
OHO
O
Castor Oil
O
O
OO
OO
OO
OO
OO
OO
OO
OO
OH
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OH
OH
Hyperlite
SBOP
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
24
Sept. 5th, 2008
Tg —Increase Polyol Chain Length
• Before we move on — collapsed foam– Avoid surfactant issues– Isolate polymer phase for examination– Small-scale sample ~15 gram total
polyolwatercatalyst isocyanate
Heated mold (75 oC, 500psi)
~1 hr curing
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
25
Sept. 5th, 2008
Making the Model Polyols
O
O
O
O
OH
OHO
O
Castor OilCH3 OH
CH3 OH CH3 OH
CH3 OH
O OH
OCH3
OCH3
O O
OH
m O
O
OH
O
O
m
O
OH m OH
OHOH
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
26
Sept. 5th, 2008
Building Up the Molecular Weight
O
O
O
O OH
R
R
O
O
O
O O
R
RO OH
O OH
OO
O
O
O O
R
RO
1K
2K
4K
3K
O
O
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OH
OH
OH
Polyether polyol-3K
Arcol
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
27
Sept. 5th, 2008
Retention TimeRetention Time (min)
20 22 24 26 28 30
The Model Polyols
Retention Time20 22 24 26 28 30
Retention Time (min)
2K3K4K
Arcol
Methyl ricinoleate
Castor oil
1K
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
28
Sept. 5th, 2008
Mn (ideal) Mn (VPO) Mn (GPC/Polyol)
Castor oil 930 930 --
2K 2010 2046 2322
3K 2934 2967 2978
4K 4054 3565 3400
Functionality # of bonds btwn OH (n)
2.9 27
2.44 64
2.18 94
2.17 114
( )(1 )g grot
cT TnN
= ∞ +Bicerano’s Correlation1:
A Model for Tg
1Bicerano et. al., J. Appl. Polym Sci. PartB: Polym Phys. (1996) 34: 2247
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
29
Sept. 5th, 2008
-100 -80 -60 -40 -20 0 20 40
Temperature (oC)
Hea
t Cap
acity
(J/g
/o C)-S
hifte
dArcol
4K
3K
2K
Castor oil
The Tg of Collapsed Foams
-120 -70 -20 30 80 130 180 230
Temperature (oC)
Hea
t Cap
acity
(J/g
/o C)
Arcol
castor oil
2K
3K
4K
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
30
Sept. 5th, 2008
How is MW Going to Change Tg ?
( )(1 )g grot
cT TnN
= ∞ +Bicerano’s Correlation1:
1Bicerano et. al., J. Appl. Polym Sci. PartB: Polym Phys. (1996) 34: 2247
0
0.1
0.2
0.3
0.4
0.5
0 0.02 0.04 0.06 0.08 0.1 0.12
1/n
0
0.1
0.2
0.3
0.4
0.5
0 0.02 0.04 0.06 0.08 0.1 0.12
1/n
0
0.1
0.2
0.3
0.4
0.5
0 0.02 0.04 0.06 0.08 0.1 0.12
1/n
PSDVBPMMA
11 ( )( )g
g rot
T cT N n
− =∞
T g(n
)
T g(
)-1
PEMA
PU flexible foam: polyether polyol
0
0.1
0.2
0.3
0.4
0 0.02 0.04 0.06 0.08 0.1 0.121/n
Arcol
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
31
Sept. 5th, 2008
Why & why?
O
O
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OH
OH
OH
Arcol
O
O
O
O O
R
RO OH
O OH
OO
O
O
O O
R
RO
2K
3K
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
32
Sept. 5th, 2008
Modification to Tg Model
• For every degree drop in Tg25% more “n” (number of bonds) is required in model polyol than in
polyether polyol
• Model polyols have an advantagePlasticizing effect of the dangling chains
( )(1 )g grot
cT TnN
= ∞ +
( )(1 )
14
g g adjrot
oadj
cT T TnN
T C
= ∞ + −
≈0
0.1
0.2
0.3
0.4
0 0.01 0.02 0.03 0.04 0.051/n
Tg(n
)/Tg(
int)-
1
T g(n
)
T g(
)-1
0
0.1
0.2
0.3
0.4
0 0.01 0.02 0.03 0.04 0.051/n
Tg(n
)/Tg(
int)-
1
T g(n
)
T g(
)-1
T g(n
)
T g(
)-1
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
33
Sept. 5th, 2008
Can We Make Flexible Foams?
1.E+06
1.E+07
1.E+08
1.E+09
1.E+10
-120 -70 -20 30 80 130 180 230
Temperature (oC)
G' (
Pa)
2K
4K
Arcol
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
34
Sept. 5th, 2008
Summary & Future Work
• Model polyols– Great potentials as the sole polyol component in
flexible foam• Building up the MW is key• Plateau modulus higher in model polyol samples than in a
polyether polyol sample
• Future work– Foaming model polyols
• Surfactants + catalysts• Foaming dynamics phase separation
– Alternative route for natural oil polyol synthesis
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
35
Sept. 5th, 2008
THE END
Questions and Comments
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
36
Sept. 5th, 2008
0.E+00
2.E+04
4.E+04
6.E+04
5 10 15 20 25 30 35
HS content (wt%)
Mod
ulus
(Psi
)
control
10% crosslinker
10% SBOP
30% SBOP
If we extend Gier's theoretical prediction
range...
HS% and Modulus
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
37
Sept. 5th, 2008
Collapsed Foam vs. Foamed Foam
1.E+02
1.E+04
1.E+06
1.E+08
-150 -50 50 150 250
Castor oil
Collapsed foam
Foamed sample
1.E+02
1.E+04
1.E+06
1.E+08
1.E+10
-150 -50 50 150 250
Temperature (oC)
G' (
Pa)
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
38
Sept. 5th, 2008
UUNIVERSITY OF NIVERSITY OF MMINNESOTAINNESOTATTHESIS DDEFENSE
39
Sept. 5th, 2008
1.E+06
1.E+07
1.E+08
1.E+09
1.E+10
-120 -70 -20 30 80 130 180 230
Temperature (oC)
G' (
Pa)
155016001650170017501800
Wavenumber (cm-1)
3K
2K
Arcol F3022
4K
Arcol
2K
3K
4K
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
O
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
O
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
O
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
O
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
O
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
O
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
O
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
OCN NCN NC
OO
HH
H
OH
O
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H
H
N NCN NC
O
H
H
O
H