02/24/2003

Polyurethanes Based on
Hydroformylated
Soybean Oil
Andrew Guo Dima Demydov
Wei Zhang Zoran Petrovic
Kansas Polymer Research Center
Pittsburg State University
1501 S. Joplin Street
Pittsburg, KS 66762
02/24/2003
Functionalization of Soybean Oil
Epoxidized
Soybean Oil
Soybean Polyaldehyde
Primary
Polyol
Polycarboxylic
Acid
Polyamines
Soybean
Oil
Secondary
Polyol
02/24/2003
Hydroformylation of Soybean Oil
O
O
O
O
O
O
CH=O
CH=O
CH=O
CH=O
Hydroformylation
O
O
O
O
O
O
CO/H
2
, Cat.
O
O
O
O
O
O
CH
2
OH
CH
2
OH
CH
2
OH
CH
2
OH
Hydrogenation
Raney Ni/H
2
Benefit: Energy efficient (100% atom economy)
Environmentally benign (0% waste)
02/24/2003
Catalyst Systems
Rh System
Soybean oil
Rh/PPh
3
H
2
/CO (1:1)
Ni/H
2
Co System
Soybean oil
Co
2
(CO)
8
H
2
/CO (1:1)
Co/H
2
02/24/2003
Catalyst Comparison
Rh System
higher yield
milder conditions
(pressure 2,000 psi,
temp. 90-100C)
require a second
metal (Ni) for
hydrogenation
Rh more costly
($1,000/Oz.)
Co System
lower yield
harsher conditions
(pressure 4,000 psi,
temp. 120-180C)
no need of a second
metal for
hydrogenation
Co cheaper
($15/lb.)
02/24/2003
Chemical and Physical Properties
of the Soy Polyols
Soy
Polyol
Conver
sion
(%)
Hydroxyl
number
(mgKOH/g)
Functio
nality
Physical
State
Rhodium
process
95% 230 4.1 viscous
liquid
Cobalt
process
67% 160 2.7 viscous
liquid
02/24/2003
GPC Traces of Hydrof. Soy Polyols
0
10
20
30
9 10 11 12 13 14
Retention Time (min)
D
e
t
e
c
t
o
r

S
i
g
n
a
l
Polyol-HF-Co
Soybean oil
Polyol-HF-Rh
02/24/2003
DSC Profiles of the Soy Polyols
-25
-20
-15
-10
-5
-80 -60 -40 -20 0 20 40 60 80 100
Temperature (C)
H
e
a
t

F
l
o
w

(
m
W
)
Soybean oil
Rh Polyol
Co Polyol
02/24/2003
02/24/2003
Soy-based Polyurethanes
OC(O)
Heat
or catalyst
Oil-based polyol
Isocyanate
+
OCN NCO
OH
OH
OH OH
OC(O)
OC(O)
OC(O)
OC(O)
OC(O)
Crosslinked polyurethane
OH
OH
02/24/2003
Glass Transition Temperatures
of the Soy Polyurethanes
Polyurethane DSC
Tg (C)
TMA
Tg (C)
DMTA
Tg (C)
Rhodium
process
48 52 57
Cobalt
process
20 21 22
02/24/2003
Stress-Strain Curves
0
10
20
30
40
50
0 20 40 60 80 100
Percent Strain (%)
S
t
r
e
s
s

(
M
P
a
)
Cobalt process
Rhodium process
02/24/2003
Tensile Properties
of the Soy Polyurethanes
Polyurethane Tensile
strength
(MPa)
Youngs
Modulus
(MPa)
Elongation
at break
(%)
Rhodium
process
38 362 17
Cobalt
process
11 13 93
02/24/2003
Property Improvement
- Effect of Crosslinker
Glass transition temperature
Tensile strength
Flexural strength
Impact Strength
02/24/2003
0
20
40
60
80
100
120
0 5 10 15 20 25 30
Amount of Glycerine (pph)
T
g

(

C
)
Effect on Tg (by DSC)
02/24/2003
0
20
40
60
80
0 5 10 15 20 25 30
Amount of Glycerine (pph)
T
e
n
s
i
l
e

S
t
r
e
n
g
t
h

(
M
P
a
)
Effect on Tensile Strength
02/24/2003
0
1000
2000
3000
0 5 10 15 20 25 30
Amount of Glycerine (pph)
F
l
e
x
u
r
a
l

M
o
d
u
l
u
s

(
M
P
a
)
Effect on Flexural Modulus
02/24/2003
Effect on Impact Strength
0
10
20
30
40
0 5 10 15 20 25 30
Amount of Glycerine (pph)
I
m
p
a
c
t

R
e
s
i
s
t
a
n
c
e

(
J
/
m
)
02/24/2003
SUMMARY
Rh-catalyzed Hydroformylation
Rigid plastic PU
Co-catalyzed Hydroformylation
Hard rubber PU
Addition of Glycerine
improves properties
02/24/2003
ACKNOWLEDGEMENT
U.S. Department of Energy
U.S. Department of Agriculture
United Soybean Board
Kansas Soybean Commission
Pittsburg State University
Noveon, Inc.
Dow ADM