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Development of Biopolymers from Soybean
OilAndrew Cascione & Nacú Hernández
Dr. Christopher Williams and Dr. Eric Cochran
1
October 10, 2012
Introduction• Asphalt cement commonly modified with
an SBS tri-block copolymer • Kraton’s® formula for asphalt modifiers
20.2 m
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
Butadiene Commodity Trends
$/ m
etric
ton
4
http://www.icis.com
Soybean Oil• Substitute of the rubbery block
• Triglycerides
• 4.6 double bonds
• Chemical modification
– Different polymerization techniques
5
$/ m
etric
ton
Butadiene and Soybean Oil Commodity Trends
6
http://www.indexmundi.com
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.
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Radical Polymerization-Mechanism4. 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.
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Polymers via Free Radical Polymerization
• 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)
Linear polymer chains
Ability to flow Will not flowSoybean Oil
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Rheological Measurements
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SBO- Homopolymer SBS Triblock copolymer
log 10 aTlog 10 aT
T
G’
200
120
160
Asphalt Polymer Blends
• Virgin PG XX-34 blended with…
• 3% Kraton SBS D1101 • 3% Kraton SBS D1118• 3% SB Diblock Biopolymer• 3% SBS Triblock Biopolymer
• Blended polymer and asphalt in shear mixer at 180°C for 2 hours
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Asphalt-PolymerBlend
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
SB Biopolymer
-35.3 -34.7 -34.7 -34.5
PG -34 PG -28
SBS Biopolymer
SBS* Biopolymer
-33.8 -33.1
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Multiple Stress Creep and Recovery(MSCR) Test – Simulated Data
γp = peak strain
γr = recovered strain
γp = unrecovered Strain
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Asphalt-PolymerBlend Temp °C
Jnr
3.2kPa-1Traffic Level Traffic Level
Criteria
XX-34 46 1.55 HHeavy (1.01 – 2.00)
SBS Biopolymer 46 0.90 VVery Heavy (0.51 – 1.00)
Asphalt-PolymerBlend Temp °C
Jnr
3.2kPa-1Traffic Level Traffic Level
Criteria
XX-34 46 1.55 HHeavy (1.01 – 2.00)
Asphalt-PolymerBlend Temp °C
Jnr
3.2kPa-1Traffic Level Traffic Level
Criteria
Multiple Stress Creep and Recovery(MSCR) Test
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Asphalt-PolymerBlend Temp °C
Jnr
3.2kPa-1Traffic Level Traffic Level
Criteria
XX-34 46 1.55 HHeavy (1.01 – 2.00)
SBS Biopolymer 46 0.90 VVery Heavy (0.51 – 1.00)
Kraton D1101 46 0.50 EExtremely Heavy (0.00 – 0.50)
SBS* Biopolymer 46 0.33 EExtremely Heavy (0.00 – 0.50)
SBS* Biopolymer20.2%
Kraton 1101 25.0%
XX-34 4.1%
SBS Biopolymer 6.6%
Passing % Recovery
Failing % Recovery
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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
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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