Biosourced Raw Materials - Moving the Farm into Polymers

2. Biosourced Raw Materials - Moving the Farm into Polymers Douglas A. Wicks Robert M. Hearin Support Foundation Professor The University of Southern Mississippi

3. Outline Overview of Polymer Science Background Examples Generation of ethanol Vegetable Oil Macromonomers Soy Bean Composites

4. School of Polymers and High Performance Materials atThe University of Southern Mississippi

5. UndergraduateEducation GraduateEducation Research CommunityOutreach/Education Graduate Education • PhD in Polymer Science and Engineering • 80 graduate students • Majority US Citizens • Diverse foreign contingent • France, China, S. Africa, Turkey, S. Korea, Spain, Brazil, Columbia, Malaysia, Poland, India, Canada

6. UndergraduateEducation GraduateEducation Research CommunityOutreach/Education Undergraduate Education • BS in Polymer Science • 4 Year degree program • 90 students • Comprehensive program • Synthesis • Coatings • Processing • Regionally drawn students • Mississippi, Louisiana, Alabama, Tennessee.

7. UndergraduateEducation GraduateEducation Research CommunityOutreach/Education Research Programs • $10MM in external funding • Federal • State • Industrial • International • National NSF Centers • Industry/Univ. Coop Res Center • Materials Research Center • Internationally recognized faculty

8. UndergraduateEducation GraduateEducation Research CommunityOutreach/Education Outreach Programs International Coatings and Formulations Institute (ICFI)

9. Polymer Science Faculty Coatings Thames Evans Urban Wicks Smith Polymer Processing Hester Moore Morgan Otaigbe

10. Polymer Science Faculty Synthesis Polymer Physics Mauritz Hoyle Lochhead Nazarenko McCormick Mathias Storey Boyes

11. Long History of Natural Products in Polymers

12. Present Project Objective Develop a concentrated acid hydrolysis process that converts softwood sawdust into sugars that can be fermented to ethanol. The process must be economical. minimize equipment cost - maximize conversion to sugars Hester

14. USM Sawdust To Sugars Mini-Plant 13 4 10 9 8 5 7 2 6 1 3 1 - motor 2 - transmission 3 - sawdust feeder 4- acid feed port 5 - twin screw extruder 6 - flow restricting orifice 7 - static mixer & water port 8 - hydrolysis reactor 9 - product cooler 10 – product collector 11 - water feed pump 12 - acid feed pump 13 – computer controller 11 12

15. Stage I: Aqueous latex Stage II: Close contact particles Stage IV: Ambient Crosslinking Stage III: Hexagonal packing Stage V: Crosslinked Film Continuous Film Formation with Solventless Latex Thames Research Group

16. Vegetable Oil Macromonomer Thames Research Group

17. Acrylate group reacts with growing polymer radicals O O H H H C O 3 H H O Residual unsaturation provides mechanism for ambient cure Alkyl moieties provide internal plasticization Castor Acrylated Monomer(CAM) Thames Research Group

18. CAM Incorporation • Variable Tg (Var-Tg) latexes • MMA:BA ratio held constant, CAM added • Iso-Tg latexes • MMA:BA:CAM ratios adjusted to achieve 5°C Tg Var-Tg CAM Latexes Iso-Tg CAM Latexes

19. Textile Latex For Military Uniforms Thames Research Group

20. Benefits • Permanent Press Uniforms • Improved wear resistance • Improved color retention • Cost savings • 100 Additional Jobs for Mississippi Thames Research Group

21. Additional Usage • 7,500 uniforms supplied to USAF for field trial • US Army testing permanent press uniforms Thames Research Group

22. Continuous Phase Synthetic Urea-formaldehyde Polyethylene Agricultural Soybean protein Lignin Reinforcements Synthetic Carbon Glass Agricultural Plant fibers Wood Environmentally Friendly CompositesComponents Thames Research Group

23. Advantages: Rapid cure time Water resistance Cure by crosslinking Disadvantages: Increasing cost Formaldehyde emissions Commercial Adhesives Prominent Adhesives • Urea-formaldehyde (UF) • Melamine-formaldehyde (MF) • Phenol-formaldehyde (PF) Thames Research Group

24. Formaldehyde • Toxic compound • Inhalation • Contact with skin • Ingestion • Irritates all parts of the respiratory system Thames Research Group

25. Soybean Adhesive Potential • Alternative to using petroleum resources • Biodegradable • Renewable • Relative low cost • Environmentally-friendly • Formaldehyde-free Thames Research Group

26. Soybean Composition Carbohydrates (35%) Protein (40%) Oils (20%) Ash (5%) http://www.nsrl.uiuc.edu http://hubcap.clemson.edu Thames Research Group

27. Formaldehyde-Free Biodegradable Wood Composites • Renewable • Biodegradable • Formaldehyde-free • Environmentally-friendly

28. Future Looking Totally Derived from Crops

29. PLLA Ionomers -Project Concept • Biodegradable ionomers (polymers containing ions) based on poly(L-lactic acid) (PLLA) • Ion groups raise glass transition temperature • Higher Tg opens new applications in food packaging and food service

30. Incorporation of Ionic Groups by Copolymerization Storey, R.F., Mullen, B.D., Melchert, K.M. J. Macromol. Sci.-Pure Appl. Chem., 2001 A38(9), 897.

31. Enhancement of Glass Transition Temperature by Ion Incorporation

32. Conclusions • Biosourced Products have a place in polymers • They can be included into high performance materials • The next generation will truly bring us back to the farm

33. Acknowledgements • The Thames Research Group • Southern Diversified Products • Professor Roger Hester • Professor Robson Storey • The US Department of Agriculture