STRUCTURE-PROPERTY

RELATIONSHIP IN VEGETABLE OIL-

BASED POLYURETHANES
Zoran S. Petrovi, Wei Zhang, Ivan Javni and
Andrew Guo
Kansas Polymer Research Center,
Pittsburg State University, Pittsburg, KS
Introduction
Thermosetting resins derived from vegetable oils
can be useful binders for composites, casting
resins for electrical applications, compression
molding compounds, foams and coatings.
They will successfully compete with petrochemical
resins on price and performance.
In this work we will describe the properties of
polyurethane resins obtained from polyols derived
from soybean oil and different isocyanates.
Advantages of soy polyurethanes
High hidrophobicity-better water resistance
Better thermo-oxidative stability
Better electrical properties
Renewable resource- stable price
Will compete with more expensive epoxy
resins
Soy Polyurethanes
polyurethane
Polyol + isocyanate
Soy Polyols by epoxidation or hydroformylation
Isocyanates: diisocyanates vs. triisocyanates;
aliphatic vs. aromatic
STRUCTURE OF SOYBEAN OIL
-OOC(CH
2
)
7
CH=CHCH
2
CH=CHCH
2
CH=CHCH
2
CH
3
linolenic - 9%
-OOC(CH
2
)
7
CH=CHCH
2
CH=CH(CH
2
)
4
CH
3
linoleic - 51%
-OOC(CH
2
)
7
CH=CH(CH
2
)
7
CH
3
oleic - 25%
-OOC(CH
2
)
16
CH
3
stearic - 15%
Average unsaturation = 4.6
(I.V. = 120-140)
O
O
O
O
O
O
POLYOL FORMATION FROM EPOXIDIZED
OILS
Epoxidized soybean oil
CH CH
OH Y
Soy polyol
(A). CH
3
OH
(B). HCl
CH CH
O
(C). HBr
(D). H
2
/Catalyst
where Y = OCH
3
, Cl, Br, or H
POLYOLS BY HYDROFORMYLATION (HF)
O
O
O
O
O
O
CH=O
CH=O
CH=O
CH=O
Hydroformylation
O
O
O
O
O
O
CO/H
2
, Rh/P
The polyaldehyde is then reduced to a polyol.
Designation and properties of
polyols
Polyol ID Reagent Conversion
Yield
Hydroxyl
Number
Equiv.
Weight
Function-
ality
Polyol Mol.
Weight, Mn
Physical
state at
(%) (mg KOH/g) (g/Equiv.) R. T.
Soy-H2 H
2
89 212 265 3.5 938 grease
Soy-Met CH
3
OH 93 199 282 3.7 1053 liquid
Soy-HCl
a
HCl 94 197 285 3.8 1071 grease
Soy-HBr
a
HBr 100 182 308 4.1 1274 grease
Soy-HF H
2
/CO 92 223 251 4.0 1004 liquid
a
- All values are calculated based on the analyzed Cl and Br contents and assuming that
each halogen is accompanied by a hydroxy group.
Viscosity of polyols vs. temperature
4.0
5.0
6.0
7.0
8.0
9.0
10.0
2.6 2.7 2.8 2.9 3.0 3.1 3.2 3.3 3.4
1/T x 1000 (K
-1
)
L
n

(

)
Soy-HF-16 Soy-Met-21 Soy-HCl Soy-HBr Soy-H2
Viscosity-temperature curves for Soy polyols and
PPO triol
0
500
1000
1500
2000
2500
3000
3500
4000
0 20 40 60 80 100 120
Temperature, deg. C
V
i
s
c
o
s
i
t
y
,

m
P
a
.
s
Soy BMW-206
Soy BMW 179
Arcol LHT-240
Formation of Polyurethane Networks by Reaction
of Polyols with Isocyanates
OC(O)
Heat
or catalyst
Oil-based polyol
Isocyanate
+
OCN NCO
OH
OH
OHOH
OC(O)
OC(O)
OC(O)
OC(O)
OC(O)
Crosslinked polyurethane
OH
OH
Stress-strain curves for PAPI/soy-
based polyurethanes
0
10
20
30
40
50
0 1 2 3 4 5 6 7 8 9 10
Strain (%)
S
t
r
e
s
s

(
M
P
a
)
Soy-H2
Soy-HCl
Soy-Met
Soy-HBr
TGA curves of soy-polyurethanes
in air
0
20
40
60
100
0 100 200 300 400 500 600
Temperature (C)
T
G
A

W
e
i
g
h
t

(
%
)
Soy-H2
Soy-HCl
Soy-HBr
80
Soy-HCl
Soy-Met
Mechanical properties of soy-based
polyurethanes
Sample ID Density
g/cm
3
DSC Glass
transition
Tensile
strength
Elongation at
break
Youngs Modulus
(C) (MPa) (%) (MPa)
Soy-HBr PAPI 1.262 75 44 7.7 1102
Soy-HBr Isonate 1.270 68 40 7.3 955
Soy-HCl PAPI 1.152 77 48 7.5 1204
Soy-HCl Isonate 1.152 73 46 8.9 1190
Soy-Met PAPI 1.113 72 45 8.4 986
Soy-Met Isonate 1.152 70 46 9.0 979
Soy-H2 PAPI 1.093 31 19 29 383
Soy-H2 Isonate 1.090 34 16 15.4 362
Soy-HF-16 PAPI 1.094 45 33.31 12.0 785
Soy-HF-16 Isonate 1.094 44 30.78 11.7 770

Conclusions (1)
Soy-based polyols displayed decreasing
density and viscosity in the following order:
SoyHBr> Soy-HCl> Soy-met> SoyH
2
> Soy-
HF.
Soy-HF and Soy-Met are liquid at RT.
The reactivity of the polyols increased in the
reverse order.
Two series of polyurethanes prepared with
two isocyanates had similar properties.
Effect of NCO/OH molar ratio
Crosslinking density of polyurethanes
networks can be varied by varying
isocyanate/hydroxyl ratio.
This ratio is directly proportional to the
crosslinking density if conversion is
complete
Relationship between number of elastically active chains
(crosslinking density) and NCO/OH molar ratio for the
system - the polyol with OH# =203 mg KOH/g and MDI
0.00E+00
2.00E-04
4.00E-04
6.00E-04
8.00E-04
1.00E-03
1.20E-03
1.40E-03
0 0.2 0.4 0.6 0.8 1 1.2
NCO/OH molar ratio
E
A
N
C
,

m
o
l
/
c
m
3
Effect of NCO/OH molar ratio for the system polyol
(OH#=203)/MDI on Tg measured by DSC (), TMA() and
DMA (+)
-20
-10
0
10
20
30
40
50
60
70
0 0.2 0.4 0.6 0.8 1 1.2
NCO/OH molar ratio
G
l
a
s
s

t
r
a
n
s
i
t
i
o
n
,

o
C
Tg = Tgo + k1/Mc= Tgo + k2(EANC)
Effect of NCO/OH ratio on density, tensile strength and elongation
0
50
100
150
200
250
0 0.2 0.4 0.6 0.8 1 1.2
NCO/OH molar ratio
T
e
n
s
i
l
e

s
t
r
e
n
g
t
h
,

M
P
a

o
r

e
l
o
n
g
a
t
i
o
n
,

%
1.06
1.065
1.07
1.075
1.08
1.085
1.09
1.095
1.1
1.105
1.11
d
e
n
s
i
t
y
,

g
/
c
m
3
elongation
Tensile strength
Dependence of tensile strength on glass transition
0
5
10
15
20
25
30
35
40
45
50
0 10 20 30 40 50 60 70
glass transition temperature,
o
C
T
e
n
s
i
l
e

s
t
r
e
n
g
t
h
,

M
P
a
Effect of crosslinking density (OH number of polyols) on
tensile strength and elongation of polyurethanes at RT
0
10
20
30
40
50
60
150 170 190 210 230 250
OH number, mg KOH/g
t
e
n
s
i
l
e

s
t
r
e
n
g
t
h
,

M
P
a
0
20
40
60
80
100
120
140
160
180
e
l
o
n
g
a
t
i
o
n
,

%
Effect of isocyanates on
properties of polyurethanes
Isocyanates: diisocyanates vs. triisocyanates;
aliphatic vs. aromatic
Polyol: Soy-206-polyol, OH# = 206 mgKOH/g.
Isocyanates
Diisocyanates:
Aromatic -MDI, TDI,
Cycloaliphatic -RMDI, IPDI,
Aliphatic - HDI
Triisocyanates: DESMODUR N100,
N3300, RFE, CB 75N
Triisocyanates
DESMODUR N100: Aliphatic Polyisocyanate,
Ew = 191. HDI based. Solvent free.
DESMODUR N3300: Aliphatic Polyisocyanate,
Ew - 195. HDI based. Solvent free.
DESMODUR RFE: Tris(p-isocyanato-phenyl)-
thiophosphate in ethyl acetate (27%). Ew =
583
DESMODUR CB 75N: TDI based aromatic
polyisocyanate in ethyl acetate (75%). Ew =
323
4 , 4 - D i p h e n y l m e t h a n e
d i i s o c y a n a t e ,
M D I ( D e s m o d u r M )

H
2
C
N C O N C O

2 , 4 : 2 , 6 - T o l u e n e
d i i s o c y a n a t e ,
T D I 8 0 : 2 0 i s o m e r
m i x t u r e
( D e s m o d u r T D 8 0 )

CH
3
N C O
N C O
CH
3
N C O
N C O
R M D I , h y d r o g e n a t e d
M D I
( D e s m o d u r W )
H
2
C
N C O N C O

I s o p h o r o n e
d i i s o c y a n t e
I P D I ( D e s m o d u r I )

N C O
N C O
H
2
C

H e x a m e t h y l e n e
d i i s o c y a n t e
H D I ( D e s m o d u r H )
N C O
N C O

D e s m o d u r N - 1 0 0 a n d
D e s m o d u r N - 3 3 0 0
t r i i s o c y a n a t e s d e r i v e d
f o r m 1 , 6 -
h e x a m e t h y l e n e
d i i s o c y a n a t e .

N
H N
C O
N C O
H N
C O
N C O
N C O

D e s m o d u r R F - E i s a
t r i s ( p - i s o c y a n a t o -
p h e n y l ) - t h i o p h o s p h a t e .
N C O
N C O
N C O
O
O
O
P
S

D e s m o d u r C B 7 5 N i s a
t r i m e t h y l o l p r o p a n e
T D I b a s e d p r e p o l y m e r
CH
3
N C O
N C
CH
3
N C O
N C
CH
3
N C O
N C
O
O
O
O
O
O


Density of polyurethanes
1.104
1.104
1.062
1.061
1.066
1.082
1.096
1.272
1.186
0.95
1
1.05
1.1
1.15
1.2
1.25
1.3
D
e
n
i
s
t
y
,

g
/
c
m
3
MDI TDI RMDI IPDI HDI N100 N3300 RFE CB 75N
Isocyanate
Ar-Dii CAl-Dii Al-Trii Ar-Trii
Al-Dii
Overlay of the E' curves
10
100
1000
10000
-100 -50 0 50 100 150
Temperature,
0
C
S
t
o
r
a
g
e

m
o
d
u
l
u
s

E
'
,

M
P
a
HDI
N3300
N100
TDI
IPDI
RMDI
MDI
RFI
CB75N
Overlay of the E" curves
0.01
0.1
1
10
100
1000
-100 -50 0 50 100 150
Temperature,
o
C
L
o
s
s

m
o
d
u
l
u
s

E
"
,

M
P
a
HDI
N3300 N100
TDI
IPDI
RMDI
MDI
RFE
CB75N
Tg by DSC
RFE
N100
26
25
93
10
47
59
50
48
N3300
CB75N
HDI
TDI
RMDI
IPDI
MDI
Al-Diis Al-Triis AR-CAl-Diis
AR-Trii
0
10
20
30
40
50
60
70
MDI TDI RMDI IPDI HDI N100 N3300 RFE CB 75N
Isocyanate
T
e
n
s
i
l
e

s
t
r
e
n
g
t
h
,

M
P
a
/
E
l
o
n
a
g
t
i
o
n
,

%
Tensile strength Elongation
Effects of different isocyanates on flexural
modulus of the soy-polyol based cast PU
resins
1380
1180
1190
1220
0
29 23
2480
2040
0
250
500
750
1000
1250
1500
1750
2000
2250
2500
MDI TDI RMDI IPDI HDI N100 N3300 RFE CB 75N
Different Isocyanates
F
l
e
x
u
r
a
l

M
o
d
u
l
u
s

[

M
P
a

]
Swelling in toluene
0
10
20
30
40
50
60
70
80
90
0 1 2 3 4 5 6 7 8 9 10 11 12
Time,Days
S
w
e
l
l
i
n
g

D
e
g
r
e
e

(

w
t
%

)
CB75N
RFE
N100
MDI
N3300
TDI
RMDI
HDI
IPDI
Conclusions (2)
New types of polyurethanes were prepared by
reacting soybean oil based polyol and different
isocyanates.
Aromatic triisocyanates give the highest strength
and modulus materials with the highest resistance
to swelling.
Aromatic and cycloaliphatic diisocynates give
materials of lower strength but higher impact
resistance.
Aliphatic isocyanates produced rubbery PURs.