Development of Biopolymers
from Soybean Oil
Andrew Cascione & Nacú Hernández
Dr. Christopher Williams and Dr. Eric Cochran
October 10, 2012
1
Introduction
• Asphalt cement commonly modified with
an SBS tri-block copolymer
• Kraton’s® formula for asphalt modifiers
0.2 mm
2
Butadiene
• Byproduct of steam cracking process
(ethylene production from crude)
– (ethylene is also produced from natural
gas which yields no butadiene)
• Gas Phase (explosion hazard)
• Polymerization of SBS
– Anionic Polymerization
• Costly/Oxygen sensitive
• Organo metalic initiators
3
$/ metric ton
Butadiene Commodity
Trends
http://www.icis.com
4
Soybean Oil
• Substitute of the rubbery block
• Triglycerides
• 4.6 double bonds
• Chemical modification
– Different polymerization techniques
5
$/ metric ton
Butadiene and Soybean Oil
Commodity Trends
http://www.indexmundi.com
6
Radical Polymerization-Mechanism
• RP consists of 4 main events:
1. Decomposition
• This step requires an Initiator capable of forming free radicals.
2. Initiation
• The decomposed free radical fragment of the initiator attacks a
monomer, yielding a monomer-free radical.
3. Propagation
• Monomer-free radical or polymer-free radicals can attack other
monomers to increase the chain length by 1.
7
Radical Polymerization-Mechanism
4. Termination
(a) Combination
– Two polymer free radicals of different lengths combine to form a
single dormant polymer.
(a)Disproportionation
– Two polymer free radicals of different lengths combine to form
two distinct dormant polymers.
8
Polymers via Free Radical
Polymerization
Linear polymer chains
Ability to flow
Soybean Oil
Will not flow
• Multifunctional nature
– Potential to crosslink with at least
one other polytriglyceride
– When a fraction of 1/N have
crosslinked (N=# of repeat units)
• Polymers reach their “gel point”
• Thermosets
(Courtesy of Richard LaRock)
9
Atom Transfer Radical Polymerization
(ATRP)
10
Atom Transfer Radical Polymerization
(ATRP)
11
Atom Transfer Radical Polymerization
(ATRP)
Soybean Oil
SB Biopolymer
SBS Biopolymer
12
Results
13
Rheological Measurements
G’
200
160
T
log 10 waT
SBO- Homopolymer
120
log 10 waT
SBS Triblock copolymer
14
Asphalt Polymer Blends
• Virgin PG XX-34 blended with…
•
•
•
•
3%
3%
3%
3%
Kraton SBS D1101
Kraton SBS D1118
SB Diblock Biopolymer
SBS Triblock Biopolymer
• Blended polymer and asphalt in shear mixer at
180°C for 2 hours
15
G* (KPa)
Unaged Binder G* (KPa)
10
9
8
7
6
5
4
3
2
1
0
XX-34
Kraton
1101
Kraton
1118
SB
Biopolymer
SBS
Biopolymer
46
52
58
Temperature °C
64
SBS*
Biopolymer
16
Unaged Binder Phase Angle
90
90
XX-34
Kraton
1101
Kraton
1118
Phase angle
85
85
80
80
SB
Biopolymer
SBS
Biopolymer
75
75
70
70
46
46
52
52
58
58
Temperature
Temperature °C
°C
64
64
SBS*
Biopolymer
17
70
High Temperature Performance Grade
Unaged
Perforamnce Grade
64
RTFO
Similar Aging
58
52
46
XX-34
Kraton
1101
Kraton
1118
SB
SBS
SBS*
18
Biopolymer Biopolymer Biopolymer
Asphalt-Polymer
Blend
Mass Loss
XX-34
0.43 %
Kraton D1101
0.77 %
Kraton D1118
0.89 %
SB Biopolymer
2.79 %
SBS Biopolymer
2.48 %
SBS* Biopolymer
0.93 %
Not So Good
Big Improvement!
19
Low Critical Temperatures
XX-34
Kraton
D1101
Kraton
D1118
-35.3
-34.7
-34.7
PG -34
SB
SBS
SBS*
Biopolymer Biopolymer Biopolymer
-34.5
-33.8
-33.1
PG -28
20
Continuous Grade Range
95.2
94.2
93.4
89.2
89.5
86.7
XX-34
Kraton
1101
Kraton
1118
SB
SBS
SBS*
Biopolymer Biopolymer Biopolymer
21
Multiple Stress Creep and Recovery
(MSCR)
Test
–
Simulated
Data
18%
γp = peak strain
16%
14%
γr = recovered strain
Strain
12%
10%
8%
6%
4%
γp = unrecovered Strain
2%
0%
0
2
4
6
Time, S
8
10
12
22
Multiple Stress Creep and Recovery
(MSCR) Test
Asphalt-Polymer
Blend
Jnr
Temp °C
3.2kPa-1
Traffic Level
H
Heavy
V
Very Heavy
Traffic Level
Criteria
XX-34
46
1.55
(1.01 – 2.00)
SBS Biopolymer
46
0.90
Kraton D1101
46
0.50
E
(0.00 – 0.50)
Extremely Heavy
SBS* Biopolymer
46
0.33
E
(0.00 – 0.50)
Extremely Heavy
(0.51 – 1.00)
23
100
90
80
Percent Recovery
70
60
Passing % Recovery
50
40
30
Kraton 1101
25.0%
SBS*
Biopolymer Failing % Recovery
SBS
20.2%
Biopolymer
20
10
XX-34
4.1%
6.6%
0
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
Non-recoverable creep compliance (Jnr3.2) kPa-1
1.8
2
24
Master Curves
• Frequency Sweep in DSR from 16 °C - 70 °C
• Fit G* data to CAM Model
• Estimated Shift Factors using WLF
• Used Shift Factors to shift δ data
25
XX-34
8.0
100
90
7.0
80
6.0
5.0
60
4.0
50
40
3.0
CAM Model Fit
2.0
30
G*
20
Phase Angle
1.0
10
0.0
0
-2.0
-1.0
0.0
1.0
2.0
3.0
Log [Reduced Frequency (ω)]
4.0
5.0
6.0
26
Phase angle
Log [G* (Pa)]
70
Kraton D1101
8.0
100
90
7.0
80
6.0
5.0
60
4.0
50
40
3.0
CAM Model Fit
2.0
30
G*
20
Phase Angle
1.0
10
0.0
0
-2.0
-1.0
0.0
1.0
2.0
3.0
Log [Reduced Frequency (ω)]
4.0
5.0
6.0
27
Phase angle
Log [G* (Pa)]
70
SBS Biopolymer
8.0
100
90
7.0
80
6.0
5.0
60
Phase angle
Log [G* (Pa)]
70
4.0
50
40
3.0
CAM Model Fit
2.0
30
G*
20
Phase Angle
1.0
10
0.0
0
-2.0
-1.0
0.0
1.0
2.0
3.0
Log [Reduced Frequency (ω)]
4.0
5.0
6.0
28
SBS* Biopolymer
8.0
100
90
7.0
80
6.0
Log [G* (Pa)]
70
5.0
Phase angle
60
4.0
50
40
3.0
CAM Model Fit
2.0
30
G*
20
Phase Angle
1.0
10
0.0
0
-2.0
-1.0
0.0
1.0
2.0
3.0
Log [Reduced Frequency (ω)]
4.0
5.0
6.0
29
XX-34 vs Kraton 1101 vs SBS* Biopolymer K X
8.0
100
90
7.0
80
6.0
5.0
60
4.0
50
40
3.0
CAM Model Fit
2.0
30
G*
20
Phase Angle
1.0
10
0.0
0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
Log [Reduced Frequency (ω)]
5.0
6.0
30
Phase angle
Log [G* (Pa)]
70
XX-34 vs Kraton 1101 vs SBS* Biopolymer K X
8.0
100
90
7.0
80
6.0
5.0
60
4.0
50
40
3.0
30
2.0
CAM Model Fit
Phase Angle
20
1.0
10
0.0
0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
Log [Reduced Frequency (ω)]
5.0
6.0
31
Phase angle
Log [G* (Pa)]
70
Next Steps
• Optimization of block copolymer
• Comprehensive experimental plan on the
blending method
• Micrographs with supporting FTIR Analysis
• HMA performance testing
• Build Pilot Plant
32
Thank You!
Any Comments or Questions?
33