1. Development of Biopolymers from Soybean Oil Andrew Cascione & Nacú Hernández Dr. Christopher Williams and Dr. Eric Cochran 1 October 10, 2012

2. Introduction Asphalt cement commonly modified with an SBS tri-block copolymer Kraton’s ® formula for asphalt modifiers 2 0.2  m

3. 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

4. Butadiene Commodity Trends $/ metric ton 4 http://www.icis.com

5. Soybean Oil Substitute of the rubbery block Triglycerides 4.6 double bonds Chemical modification – Different polymerization techniques 5

6. $/ metric ton Butadiene and Soybean Oil Commodity Trends 6 http://www.indexmundi.com

7. 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

8. 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

9. 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 flow Soybean Oil 9

10. Atom Transfer Radical Polymerization (ATRP) 10

11. Atom Transfer Radical Polymerization (ATRP) 11

12. Atom Transfer Radical Polymerization (ATRP) 12 SB Biopolymer SBS Biopolymer Soybean Oil

13. Results 13

14. Rheological Measurements 14 SBO- Homopolymer SBS Triblock copolymer log 10  aT T G’ 200 120 160

15. 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 15

16. Unaged Binder G* (KPa) 16

17. Unaged Binder Phase Angle 17

18. High Temperature Performance Grade 18

19. Asphalt-Polymer Blend Mass Loss XX-340.43 % Kraton D11010.77 % Kraton D11180.89 % SB Biopolymer2.79 % SBS Biopolymer2.48 % SBS* Biopolymer0.93 % Not So Good Big Improvement! 19

20. Low Critical Temperatures XX-34 Kraton D1101 Kraton D1118 SB Biopolymer -35.3-34.7 -34.5 PG -34 PG -28 SBS Biopolymer SBS* Biopolymer -33.8-33.1 20

21. Continuous Grade Range 86.7 94.2 89.589.2 95.2 93.4 21

22. Multiple Stress Creep and Recovery (MSCR) Test – Simulated Data γ p = peak strain γ r = recovered strain γ p = unrecovered Strain 22

23. Asphalt-Polymer Blend Temp °C J nr 3.2kPa -1 Traffic Level Traffic Level Criteria XX-34461.55 H Heavy (1.01 – 2.00) SBS Biopolymer460.90 V Very Heavy (0.51 – 1.00) Asphalt-Polymer Blend Temp °C J nr 3.2kPa -1 Traffic Level Traffic Level Criteria XX-34461.55 H Heavy (1.01 – 2.00) Asphalt-Polymer Blend Temp °C J nr 3.2kPa -1 Traffic Level Traffic Level Criteria Multiple Stress Creep and Recovery (MSCR) Test 23 Asphalt-Polymer Blend Temp °C J nr 3.2kPa -1 Traffic Level Traffic Level Criteria XX-34461.55 H Heavy (1.01 – 2.00) SBS Biopolymer460.90 V Very Heavy (0.51 – 1.00) Kraton D1101460.50 E Extremely Heavy (0.00 – 0.50) SBS* Biopolymer460.33 E Extremely Heavy (0.00 – 0.50)

24. SBS * Biopolymer 20.2% Kraton 1101 25.0% XX-34 4.1% SBS Biopolymer 6.6% Passing % Recovery Failing % Recovery 24

25. 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

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32. 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

33. Thank You! Any Comments or Questions? 33