1 / 38

Sustainable Polymers: Thermosets from Agricultural Oils

Sustainable Polymers: Thermosets from Agricultural Oils. Michael R. Kessler. School of Mechanical and Materials Engineering Washington State University. Co-authors: Richard Larock, Yongshang Lu, Ying Xia, Rafael Quirino, Tom Garrison, and Prashanth Badrinarayanan.

bach
Download Presentation

Sustainable Polymers: Thermosets from Agricultural Oils

An Image/Link below is provided (as is) to download presentation Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author. Content is provided to you AS IS for your information and personal use only. Download presentation by click this link. While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server. During download, if you can't get a presentation, the file might be deleted by the publisher.

E N D

Presentation Transcript

  1. Sustainable Polymers: Thermosets from Agricultural Oils Michael R. Kessler School of Mechanical and Materials Engineering Washington State University Co-authors: Richard Larock, Yongshang Lu, Ying Xia, Rafael Quirino, Tom Garrison, and Prashanth Badrinarayanan

  2. Polymer Composites Research Group Funding: • National Science Foundation • Consortium for Plant Biotechnology Research • ISU Plant Sciences Institute, Grow Iowa Values Fund • UNI Recycling and Reuse Tech. Transfer Center • Industry

  3. Overview of Research Multi-functional composites Processing and characterization of polymer composites Bio-renewable polymers and composites Polymer Nano-composites Polymer matrix composites for extreme environments Rheology and thermal analysis

  4. Overview of Research Multi-functional composites Processing and characterization of polymer composites Bio-renewable polymers and composites Polymer Nano-composites Polymer matrix composites for extreme environments Rheology and thermal analysis

  5. Overview of Research Multi-functional composites Processing and characterization of polymer composites Bio-renewable polymers and composites Polymer Nano-composites Polymer matrix composites for extreme environments Rheology and thermal analysis Nearly two orders of magnitude increase in toughness with just 0.4 wt% Carbon Nanotubes

  6. Overview of Research Multi-functional composites Structural Capacitors Processing and characterization of polymer composites Bio-renewable polymers and composites Polymer Nano-composites Self-healing Composites Polymer matrix composites for extreme environments Rheology and thermal analysis

  7. Overview of Research Multi-functional composites Processing and characterization of polymer composites Bio-renewable polymers and composites Polymer Nano-composites Polymer matrix composites for extreme environments Rheology and thermal analysis

  8. Outline • Plastics from vegetable oils (thermosets) • Free radical polymerization • Cationic polymerization • Ring-opening metathesis polymerization • Composites • Polyurethane Coatings

  9. Advantages of Natural Oils • Readily available on a huge scale. • Very inexpensive. • Natural and renewable. • High purity. • Relatively high molecular weight. • Can be genetically engineered. • Many structurally related natural oils are readily available. Million Metric Tons Billion Pounds U.S. Soybean Oil Production. Source: USDA

  10. Soybean Oil Structure Oleic acid 22% Linoleic acid 54% Linolenic acid 8%

  11. Natural and Conjugated Oils OilC=C Bonds% Composition Conjugated No. C18:1 C18:2 C18:3 no no yes no yes yes Regular soy oil (SOY) LoSatSoy oil (LSS)Conjugated LSS (CLS)Linseed oil (LIN) Conjugated linseed oil (CLIN) Tung oil (TUN) 4.5 5.1 5.1 5.8 5.8 8.2 22 20 20 19 19 5 54 64 64 15 15 7 8 9 9 57 57 85a a-Eleostearic acid (9,11,13-octadecatrienoic acid) ?

  12. Free Radical Polymerization

  13. Free Radical Polymerization of Conjugated Soybean Oil DCP = dicyclopentadiene

  14. Cationic Polymerization

  15. Mechanical Properties of Soybean Oil Polymers

  16. Polymers from Other Vegetable Oils • All oils have a triglyceride structure composed primarily of oleic acid, linoleic acid and linolenic acid. • Generally, higher unsaturation results in a plastic with higher mechanical properties. Percentages of reacted oil

  17. Polymers from Other Vegetable Oils • The agricultural oil-based polymers exhibit characteristics ranging from soft to tough plastics. • Generally, a higher degree of unsaturation in the oil results in a plastic with higher mechanical properties.

  18. Ring Opening Metathesis Polymerization of Oils Dilulin  Dilulin is found to have approximately 1 bicyclic unit per triglyceride.  1H NMR and FTIR indicate the presence of norbornene-like hydrogens.

  19. Ring Opening Metathesis Polymerization of Oils Characteristics of Oil-Based ROMP Copolymers υe , crosslink density according to rubber theory of elasticity E', storage modulus at 25 oC Tmax, temperature of maximum degradation

  20. Ring Opening Metathesis Polymerization of Oils

  21. Ring Opening Metathesis Polymerization of Oils • Crosslink densities have been calculated at temperatures 50 oC above the Tg according to the equation: • An increase in the amount of NCA increases the Tg, the crosslink density, and the room temperature storage modulus

  22. Outline • Plastics from vegetable oils (thermosets) • Free radical polymerization • Cationic polymerization • Ring-opening metathesis polymerization • Composites • Polyurethane Coatings

  23. Soy-Glass Fiber Composites Mechanical properties • Incorporating glass fiber into the soy-based polymer results in good composites with improved properties. • Increasing crosslinking of the polymer matrix can dramatically increase the mechanical properties.  Fiber surface modification and compatibilization efforts are currently underway

  24. Soy-Organomodified Clay Nanocomposites Mechanical properties • 1-2 wt % clay can significantly increase the mechanical properties. • CLS affords better mechanical properties than CSOY.

  25. Linseed Oil-Natural Fiber Composites CLIN-Woodflour CLIN-Kenaf Fiber Mechanical properties • The modulus increases linearly with increasing natural fiber content. • The strength decreases a bit due to poor interfacial adhesion. Fiber surface modification and compatibilization efforts are underway

  26. Tung Oil-Spent Germ Biocomposites Matrix: TUN50-BMA35-DVB15-TBPO5 Fillers: Spent Germ (~ 50 wt %) Tensile test Flexural test • Incorporating spent germ can significantly increase the mechanical properties • Particle size plays an important role in improving the materials performance

  27. Corn Stover Biocomposites Matrix: CSOY50-BMA35-DVB15-TBPO5 Filler: 2 mm Corn Stover Matrix: (CSOY or CLIN)50-(BMA + DVB)50-TBPO5 Filler: 2 mm Corn Stover (70 wt %) • Increasing the corn stover, up to 70 wt %, results in a considerable increase in the strength and stiffness of the composites. • A higher crosslinked matrix, achieved by increasing the amount of the crosslinker, DVB, or replacing CSOY with the more highly unsaturated oil CLIN gives enhanced mechanical properties.

  28. Wheat Straw Biocomposites Matrix: CLIN50-BMA35-DVB15-TBPO5 Filler: 2 mm Wheat Straw Matrix: (CLIN)50-(BMA + MA)35-DVB15-TBPO5 Filler: 2 mm Wheat Straw (80 wt %) • Good mechanical properties can be maintained using as much as 80 wt % of wheat straw. • Maleic anhydride (MA) is an effective compatibilizer between the filler and matrix and significant increases in the mechanical properties result by the addition of MA.

  29. Outline • Plastics from vegetable oils (thermosets) • Free radical polymerization • Cationic polymerization • Ring-opening metathesis polymerization • Composites • Polyurethane Coatings

  30. Vegetable Oil-Based Dispersions

  31. Vegetable Oil-Based Dispersions (4.0) (2.8) (2.4)

  32. Vegetable Oil-Based Dispersions • The Tg of the SPU films increases linearly with an increase in the OH functionality. • The mechanical properties of the SPU films increase with the OH functionality. • The mechanical properties of the SPU films change from those of an elastomer to a ductile polymer and eventually to a hard plastic with an increase in the OH functionality.

  33. Vegetable Oil-Based Cationic PU Dispersions

  34. Vegetable Oil-Based Cationic PU Dispersions 2 3 4 6 5 Zone of inhibition for Salmonella Minnesota R613. 1) acetic acid control, 2) PU-MDEA, 3) PU-EDEA, 4) PU-PDE, 5) PU-MDEA-TEA, 6) PU-EDTE. • PU-MDEA (2) and PU-EDEA (3) show best antibacterial properties, because their smaller methyl and ethyl side chains on N atoms allow greater penetration of these polymers into cells.

  35. Summary • Industrially promising biopolymers ranging from elastomers to rigid plastics have been prepared. • These biomaterials have excellent thermal and mechanical properties. • Work with other comonomers, oils and processes is underway. • Biocomposites can be made from a variety of materials. • Work on biobased coatings and adhesives is promising.

  36. Questions?/Discussion

  37. Oil Linseed Walnut Safflower Sunflower Soy Corn Sesame Peanut % Conjugation 100 85 91 82 100 78 74 70 Extra Slide 1 Conjugation of Natural Oils J. Am. Oil. Chem. Soc. 78, 447 (2001)

  38. Damping Properties of Soybean Oil Polymers

More Related